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ZnTiO3/TiO2 composite photocatalysts were synthesized via the sol–gel technique, and the impact of varying heat treatment temperatures (470, 570, 670 °C) on their crystalline arrangement, surface morphology, elemental composition, chemical state, specific surface area, optical characteristics, and photocatalytic efficacy was systematically investigated. The outcomes revealed that, as the temperature ascends, pure TiO2 undergoes a transition from anatase to rutile, ultimately forming a hybrid crystal structure at 670 °C. The incorporation of ZnTiO3 engenders a reduction in the TiO2 grain dimensions and retards the anatase-to-rutile phase transition. Consequently, the specimens manifest a composite constitution of anatase and ZnTiO3. In contrast, for pure TiO2, the specimen subjected to 670 °C annealing demonstrates superior photocatalytic performance due to its amalgamated crystal arrangement. The degradation efficacy of methylene blue (MB) aqueous solution attains 91% within a 60-min interval, with a calculated first-order reaction rate constant of 0.039 min−1. Interestingly, the ZnTiO3/TiO2 composite photocatalysts exhibit diminished photocatalytic activity in comparison to pristine TiO2 across all three temperature variations. Elucidation of the photocatalytic mechanism underscores that ZnTiO3 coupling augments the generation of photogenerated charge carriers. Nonetheless, concurrently, it undermines the crystalline integrity of the composite, yielding an excess of amorphous constituents that impede the mobility of photoinduced carriers. This dual effect also fosters escalated recombination of photogenerated charges, culminating in diminished quantum efficiency and reduced photocatalytic performance.

Osteoporosis (OP) is distinguished by a reduction in bone mass and degradation of bone micro-structure, frequently resulting in fractures. As the geriatric demographic expands, the incidence of affected individuals progressively rises, thereby exerting a significant impact on the quality of life experienced by individuals. The flavonoid compound hesperidin has been subject to investigation regarding its effects on skeletal health, albeit the precise mechanisms through which it operates remain ambiguous. This study utilized network pharmacology to predict the core targets and signaling pathways implicated in the anti-OP properties of hesperidin. Molecular docking and molecular dynamics simulations were employed to confirm the stability of the interaction between hesperidin and the core targets. The effects of hesperidin on osteoblastic cells MC3T3-E1 were assessed using MTT, ELISA, alkaline phosphatase assay, and RT-qPCR techniques. Furthermore, in vivo experiments were conducted to determine the potential protective effects of hesperidin on zebrafish bone formation and oxidative stress response. The results demonstrate that network pharmacology has identified 10 key target points, significantly enriched in the estrogen signaling pathway. Hesperidin exhibits notable promotion of MC3T3-E1 cell proliferation and significantly enhances ALP activity. ELISA measurements indicate an elevation in NO levels and a reduction in IL-6 and TNF-α. Moreover, RT-qPCR analysis consistently reveals that hesperidin significantly modulates the mRNA levels of ESR1, SRC, AKT1, and NOS3 in MC3T3-E1 cells. Hesperidin promotes osteogenesis and reduces oxidative stress in zebrafish. Additionally, we validate the stable and tight binding of hesperidin with ESR1, SRC, AKT1, and NOS3 through molecular dynamics simulations. In conclusion, our comprehensive analysis provides evidence that hesperidin may exert its effects on alleviating OP through the activation of the estrogen signaling pathway via ESR1. This activation leads to the upregulation of SRC, AKT, and eNOS, resulting in an increase in NO levels. Furthermore, hesperidin promotes osteoblast-mediated bone formation and inhibits pro-inflammatory cytokines, thereby alleviating oxidative stress associated with OP.

Since Hydrogen Sulfide (H2S) was recognized as a gas transmitter, its detection and quantification have become a hot research topic among chemists and biologists. In this area, fluorescent probes have shown great advantages: fast and strong response, low detection limit and easy manipulation. Here we developed a new fluorescent probe that detected H2S selectively among various bioactive and inorganic salts. This probe was based on the core structure of fluorescein and reacted with H2S through azide-reduction. Great linearity was achieved correlating fluorescence intensity and H2S concentrations in solution. The detection of H2S in cancer cells was also achieved.

Crystalline borates have received great attention due to their various structures and wide applications. For a long time, the corner-sharing B–O unit is considered a basic rule in borate structural chemistry. The Dy4B6O15 synthesized under high-pressure is the first oxoborate with edge-sharing [BO4] tetrahedra, while the KZnB3O6 is the first ambient pressure borate with the edge-sharing [BO4] tetrahedra. The edge-sharing connection modes greatly enrich the structural chemistry of borates and are expected to expand new applications in the future. In this review, we summarize the recent progress in crystalline borates with edge-sharing [BO4] tetrahedra. We discuss the synthesis, fundamental building blocks, structural features, and possible applications of these edge-sharing borates. Finally, we also discuss the future perspectives in this field.

Ag/TiO2/muscovite (ATM) composites were prepared by the sol–gel method and the effects of Ag modification on the structure and photocatalytic performance were investigated. The photocatalysts were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area (BET), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectra (FTIR), photoluminescence spectra (PL) and ultraviolet–visible diffuse reflectance spectra (DRS). The photocatalytic activity of the obtained composites was evaluated by taking 100 mL (10 mg/L) of Rhodamine B (RhB) aqueous solution as the target pollutant. The muscovite (Mus) loading releases the agglomeration of TiO2 particles and the specific surface area increases from 17.6 m2/g (pure TiO2) to 39.5 m2/g (TiO2/Mus). The first-order reaction rate constant increases from 0.0009 min−1 (pure TiO2) to 0.0074 min−1 (150%TiO2/Mus). Ag element exists in elemental silver. The specific surface area of 1-ATM further increases to 66.5 m2/g. Ag modification promotes the separation of photogenerated electrons and holes and increases the visible light absorption. 1%Ag-TiO2/Mus (1-ATM) exhibits the highest photocatalytic activity. After 100 min, the rhodamine B (RhB) degradation degrees of PT, 150%TiO2/Mus and 1-ATM are 10.4%, 48.6% and 90.6%, respectively. The first-order reaction rate constant of 1-ATM reaches 0.0225 min−1, which is 25 times higher than that of pure TiO2.

To bridge the technical gap of heterojunction induction control in conventional semiconductor photocatalysts, a method of regulating the growth of heterojunctions utilizing biomimetic structures was designed to prepare a series of Bi2WO6/Bi2O3 vertical heterojunction nanocomposites for the disposal of environmentally hazardous tetracycline wastewater difficult to degrade by conventional microbial techniques. Porous Bi2O3 precursors with high-energy crystalline (110) dominant growth were produced using the sunflower straw bio-template technique (SSBT). Bi2WO6 with a (131) plane grew preferentially into 2.8 to 4 nm pieces on the (110) plane of Bi2O3, causing a significant density reduction between Bi2WO6 pieces and a dimensional decrease in the agglomerated Bi2WO6 spheres from 3 μm to 700 nm since Bi2WO6 grew on the structure of the biomimetic Bi2O3. The optimal 1:8 Bi2WO6/Bi2O3 coupling catalyst was obtained via adapting the ratio of the two semiconductors, and the coupling ratio of 1:8 minimized the adverse effects of the overgrowth of Bi2WO6 on degradation performance by securing the quantity of vertical heterojunctions. The material degradation reaction energy barrier and bandgap were significantly reduced by the presence of a large number of vertical heterojunction structures, resulting in a material with lower impedance and higher electron–hole separation efficiency; thus, the degradation efficiency of 1:8 Bi2WO6/Bi2O3 for tetracycline hydrochloride reached 99% within 60 min. In conclusion, this study not only successfully synthesized a novel photocatalyst with potential applications in water pollution remediation but also introduced a pioneering approach for semiconductor-driven synthesis.

Allantoinase (ALLase; EC 3.5.2.5) possesses a binuclear metal center in which two metal ions are bridged by a posttranslationally carbamylated lysine. ALLase acts as a key enzyme for the biogenesis and degradation of ureides by catalyzing the conversion of allantoin into allantoate. Biochemically, ALLase belongs to the cyclic amidohydrolase family, which also includes dihydropyrimidinase, dihydroorotase, hydantoinase (HYDase), and imidase. Previously, the crystal structure of ALLase from Escherichia coli K-12 (EcALLase-K12) was reported; however, the two active site loops crucial for substrate binding were not determined. This situation would limit further docking and protein engineering experiments. Here, we solved the crystal structure of E. coli BL21 ALLase (EcALLase-BL21) at a resolution of 2.07 Å (PDB ID 8HFD) to obtain more information for structural analyses. The structure has a classic TIM barrel fold. As compared with the previous work, the two missed active site loops in EcALLase-K12 were clearly determined in our structure of EcALLase-BL21. EcALLase-BL21 shared active site similarity with HYDase, an important biocatalyst for industrial production of semisynthetic penicillin and cephalosporins. Based on this structural comparison, we discussed the functional role of the two active site loops in EcALLase-BL21 to better understand the substrate/inhibitor binding mechanism for further biotechnological and pharmaceutical applications.

Houttuyniae herba has a long history of medicinal and edible homology in China. It has the functions of clearing heat and detoxifying, reducing swelling and purulent discharge, diuresis, and relieving gonorrhea. It is mainly distributed in the central, southeastern, and southwestern provinces of China. Houttuyniae herba has been designated by the National Ministry of Health of China as a dual-use plant for both food and medicine. Comprising volatile oils, flavonoids, and alkaloids as its primary constituents, Houttuyniae herba harbors aristolactams, a prominent subclass of alkaloids. Notably, the structural affinity of aristolactams to aristolochic acids is discernible, the latter known for its explicit toxicological effects. Additionally, the safety study on Houttuyniae herba mainly focused on the ethanol, methanol, or aqueous extract. In this study, both zebrafish and mice were used to evaluate the acute toxicity of the total alkaloids extracts from Houttuyniae herba (HHTAE). The zebrafish experiment showed that a high concentration (0.1 mg/mL) of HHTAE had a lethal effect on zebrafish embryos. Furthermore, the mice experiment results showed that, even at a higher dose of 2000 mg/kg, HHTAE was not toxic. In conclusion, HHTAE was of low safety risk. [ABSTRACT FROM AUTHOR]

Bitespiramycin, has been shown to have a therapeutic effect against respiratory tract inflammation, including a potential effect against COVID-19. A current clinical trial in China showed that bitespiramycin was an effective treatment for severe pneumonia and intracranial infection. However, there is lack of an analytical method to elucidate the distribution of bitespiramycin. In this study, a highly sensitive, rapid and reliable UPLC–MS/MS method was developed to comprehensively characterize the bitespiramycin distribution in various bio-samples, which is significantly improved upon the published work. A rapid sample preparation method was developed by using n-butanol as the solvent to extract bitespiramycin from different bio-samples. The extract was then directly analyzed by UPLC–MS/MS coupled with an alkaline-resistant column after centrifugation which avoids the time-consuming concentration process under nitrogen and redissolution. The method was employed to accurately quantify bitespiramycin and its metabolites in rat plasma, tissues, and human cerebrospinal fluid. Notably, the presence of bitespiramycin and its metabolites was identified for the first time in various rat organs including brain, testis, bladder and prostate as well as in human cerebrospinal fluid. This newly developed approach shows great promise for drug distribution assays including other antibiotics and can help elucidate the ADME of bitespiramycin. [ABSTRACT FROM AUTHOR]

Molecular photoswitches are considered to be important candidates in the field of solar energy storage due to their sensitive and reversible bidirectional optical response. Nevertheless, it is still a daunting challenge to design a molecular photoswitch to improve the low solar spectrum utilization and quantum yields while achieving charging and discharging of heat without solvent assistance. Herein, a series of visible-light-driven ethylene-bridged azobenzene (b-Azo) chromophores with different alkyne substituents which can undergo isomerization reactions promoted in both directions by visible light are reported. Their visible light responsiveness improves their solar spectrum utilization while also having high quantum yields. In addition, as the compounds are liquids, there is no need to dissolve the compounds in order to exploit this switching. The photoisomerization of b-Azo can be adjusted by alkyne-related substituents, and hexyne-substituted b-Azo is able to store and release photothermal energy with a high density of 106.1 J·g−1, and can achieve a temperature increase of 1.8 °C at a low temperature of −1 °C.

The water-resistant characteristics of ultraviolet crosslinked polyethylene (UV-XLPE) are investigated specially for the dependence on the hydrophilicities of auxiliary crosslinkers, which is significant to develop high-voltage insulating cable materials. As auxiliary crosslinking agents of polyethylene, triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA), and N,N′-m-phenylenedimaleimide (HAV2) are individually adopted to prepared XLPE materials with the UV-initiation crosslinking technique, for the study of water-tree resistance through the accelerating aging experiments with water blade electrode. The stress–strain characteristics and dynamic viscoelastic properties of UV-XLPE are tested by the electronic tension machine and dynamic thermomechanical analyzer. Monte Carlo molecular simulation is used to calculate the interaction parameters and mixing energy of crosslinker/water binary systems to analyze the compatibility between water and crosslinker molecules. Water-tree experiments verify that XLPE-TAIC represents the highest ability to inhibit the growth of water-trees, while XLPE-HAV2 shows the lowest resistance to water-trees. The stress–strain and viscoelastic properties show that the concentration of molecular chains connecting the adjacent lamellae in amorphous phase of XLPE-HAV2 is significantly higher than that of XLPE-TAIC and XLPE-TMPTMA. The molecular simulation results demonstrate that TAIC/water and TMPTMA/water binary systems possess a higher hydrophilicity than that of HAV2/water, as manifested by their lower interaction parameters and mixing free energies. The auxiliary crosslinkers can not only increase the molecular density of amorphous polyethylene between lamellae to inhibit water-tree growth, but also prevent water molecules at insulation defects from agglomerating into micro-water beads by increasing the hydrophilicity of auxiliary crosslinkers, which will evidently reduce the damage of micro-water beads on the amorphous phase in UV-XLPE. The better compatibility of TAIC and water molecules is the dominant reason accounting for the excellent water resistance of XLPE-TAIC.

Space charge characteristics of cross-linked polyethylene (XLPE) at elevated temperatures have been evidently improved by the graft modifications with ultraviolet (UV) initiation technique, which can be efficiently utilized in industrial cable manufactures. Maleic anhydride (MAH) of representative cyclic anhydride has been successfully grafted onto polyethylene molecules through UV irradiation process. Thermal stimulation currents and space charge characteristics at the elevated temperatures are coordinately analyzed to elucidate the trapping behavior of blocking charge injection and impeding carrier transport which is caused by grafting MAH. It is also verified from the first-principles calculations that the bound states as charge carrier traps can be introduced by grafting MAH onto polyethylene molecules. Compared with pure XLPE, the remarkably suppressed space charge accumulations at high temperatures have been achieved in XLPE-g-MAH. The polar groups on the grafted MAH can provide deep traps in XLPE-g-MAH, which will increase charge injection barrier by forming a charged layer of Coulomb-potential screening near electrodes and simultaneously reduce the electrical mobility of charge carriers by trap-carrier scattering, resulting in an appreciable suppression of space charge accumulations inside material. The exact consistence of experimental results with the quantum mechanics calculations demonstrates a promising routine for the modification strategy of grafting polar molecules with UV initiation technique in the development of high-voltage DC cable materials.

Water-tree resistances of styrene block copolymer/polypropylene (SEBS/PP) composites are investigated by characterizing crystallization structures in correlation with the dynamic mechanical properties to elucidate the micro-structure mechanism of improving insulation performances, in which the accelerated aging experiments of water trees are performed with water-knife electrodes. The water-tree morphology in spherulites, melt-crystallization characteristics and lamella structures of the composite materials are observed and analyzed by polarizing microscopy (PLM), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), respectively. Dynamic relaxation and stress-strain characteristics are specifically studied by means of a dynamic thermomechanical analyzer (DMA) and electronic tension machine, respectively. No water-tree aging occurs in both the highly crystalline PP and the noncrystalline SEBS elastomer, while the water trees arising in SEBS/PP composites still has a significantly lower size than that in low-density polyethylene (LDPE). Compared with LDPE, the PP matrix of the SEBS/PP composite represent a higher crystallinity with a larger crystallization size in consistence with its higher mechanical strength and lower dynamic relaxation loss. SEBS molecules agglomerate as a “island” phase, and PP molecules crystallize into thin and short lamellae in composites, leading to the blurred spherulite boundary and the appreciable slips between lamellae under external force. The high crystallinity of the PP matrix and the strong resistance to slips between lamellae in the SEBS/PP composite essentially account for the remarkable inhibition on water-tree growth.

In order to inhibit the outward-migrations of photo-initiator molecules in the ultraviolet-initiated crosslinking process and simultaneously improve the crosslinking degree and dielectric properties of crosslinked polyethylene (XLPE) materials, we have specifically developed surface-modified-SiO2/XLPE nanocomposites with the silica nanofillers that have been functionalized through chemical surface modifications. With the sulfur-containing silanes and 3-mercaptopropyl trimethoxy silane (MPTMS), the functional monomers of auxiliary crosslinker triallyl isocyanurate (TAIC) have been successfully grafted on the silica surface through thiol–ene click chemistry reactions. The grafted functional groups are verified by molecular characterizations of Fourier transform infrared spectra and nuclear magnetic resonance hydrogen spectra. Scanning electronic microscopy (SEM) indicates that the functionalized silica nanoparticles have been filled into polyethylene matrix with remarkably increased dispersivity compared with the neat silica nanoparticles. Under ultraviolet (UV) irradiation, the high efficient crosslinking reactions of polyethylene molecules are facilitated by the auxiliary crosslinkers that have been grafted onto the surfaces of silica nanofillers in polyethylene matrix. With the UV-initiated crosslinking technique, the crosslinking degree, insulation performance, and space charge characteristics of SiO2/XLPE nanocomposites are investigated in comparison with the XLPE material. Due to the combined effects of the high dispersion of nanofillers and the polar-groups of TAIC grafted on the surfaces of SiO2 nanofillers, the functionlized-SiO2/XLPE nanocomposite with an appropriate filling content represents the most preferable crosslinking degree with multiple improvements in the space charge characteristics and direct current dielectric breakdown strength. Simultaneously employing nanodielectric technology and functional-group surface modification, this study promises a modification strategy for developing XLPE nanocomposites with high mechanical and dielectric performances.

Crystalline borates have received great attention due to their various structures and wide applications. For a long time, the corner-sharing B–O unit is considered a basic rule in borate structural chemistry. The Dy4B6O15 synthesized under high-pressure is the first oxoborate with edge-sharing [BO4] tetrahedra, while the KZnB3O6 is the first ambient pressure borate with the edge-sharing [BO4] tetrahedra. The edge-sharing connection modes greatly enrich the structural chemistry of borates and are expected to expand new applications in the future. In this review, we summarize the recent progress in crystalline borates with edge-sharing [BO4] tetrahedra. We discuss the synthesis, fundamental building blocks, structural features, and possible applications of these edge-sharing borates. Finally, we also discuss the future perspectives in this field. [ABSTRACT FROM AUTHOR]

Crude herbs of Daphne genkwa (CHDG) are often used in traditional Chinese medicine to treat scabies baldness, carbuncles, and chilblain owing to their significant purgation and curative effects. The most common technique for processing DG involves the use of vinegar to reduce the toxicity of CHDG and enhance its clinical efficacy. Vinegar-processed DG (VPDG) is used as an internal medicine to treat chest and abdominal water accumulation, phlegm accumulation, asthma, and constipation, among other diseases. In this study, the changes in the chemical composition of CHDG after vinegar processing and the inner components of the changed curative effects were elucidated using optimized ultrahigh-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). Untargeted metabolomics, based on multivariate statistical analyses, was also used to profile differences between CHDG and VPDG. Eight marker compounds were identified using orthogonal partial least-squares discrimination analysis, which indicated significant differences between CHDG and VPDG. The concentrations of apigenin-7-O-β-d-methylglucuronate and hydroxygenkwanin were considerably higher in VPDG than those in CHDG, whereas the amounts of caffeic acid, quercetin, tiliroside, naringenin, genkwanines O, and orthobenzoate 2 were significantly lower. The obtained results can indicate the transformation mechanisms of certain changed compounds. To the best of our knowledge, this study is the first to employ mass spectrometry to detect the marker components of CHDG and VPDG. [ABSTRACT FROM AUTHOR]

In order to improve the mechanical and dielectric properties of radome cyanate, a synergistic reinforcement method is employed to develop a resin-based ternary-composite with high heat-resistance and preferable radar-band transmission, which is expected to be applied to fabricate radomes capable of resisting high temperature and strong electric field. According to copolymerization characteristics and self-curing mechanism, epoxy resin (EP) and bismaleimide (BMI) are employed as reinforcements mixed into a cyanate ester (CE) matrix to prepare CE/BMI/EP composites of a heat-resistant radome material by high-temperature viscous-flow blending methods under the catalysis of aluminum acetylpyruvate. The crystallization temperature, transition heat, and reaction rate of cured polymers were tested to analyze heat-resistance characteristics and evaluate material synthesis processes. Scanning electron microscopy was used to characterize the micro-morphology of tensile fracture, which was combined with the tensile strength test and dynamic thermomechanical analysis to investigate the composite modifications on tenacity and rigidity. Weibull statistics were performed to analyze the experimental results of the dielectric breakdown field, and the dielectric-polarization and wave-transmission performances were investigated according to alternative current dielectric spectra. Compared with the pure CE and the CE composites individually reinforced by EP or BMI, the CE/BMI/EP composite acquires the most significant amelioration in both the mechanical and electrical insulation performances as indicated by the breaking elongation and dielectric breakdown strength being simultaneously improved by 40%, which are consistently manifested by the obviously increased transverse lines uniformly distributed on the fracture cross-section. Furthermore, the glass-transition temperature of CE/BMI/EP composite reaches the highest values of nearly 300 °C, with the relative dielectric constant and dielectric loss being mostly reduced to less than 3.2 and 0.01, respectively. The experimental results demonstrate that the CE/BMI/EP composite is a highly-qualified wave-transmission material with preferences in mechanical, thermostability, and electrical insulation performances, suggesting its prospective applications in low-frequency transmittance radomes.

Schisantherin A is an active ingredient originating from Schisandra chinensis (Turcz.) which has hepatoprotective and anti-oxidation activities. In this study, in vitro metabolisms investigated on rat liver microsomes (RLMs) and in vivo metabolisms explored on male Sprague Dawley rats of Schisantherin A were tested, respectively. The metabolites of Schisantherin A were identified using ultra-high-performance liquid chromatography coupled with hybrid triple quadrupole time-of-flight mass spectrometry (UHPLC-Q-TOF-MS/MS). Based on the method, 60 metabolites were successfully identified and structurally characterized including 48 phase-I and 12 phase-II metabolites. Among the metabolites, 45 metabolites were reported for the first time. Moreover, 56 and eight metabolites were detected in urine and bile and 19 metabolites were identified in rats’ plasma. It demonstrated that hepatic and extra-hepatic metabolic pathways were both involved in Schisantherin A biotransformation in rats. Five in vitro metabolites were structurally characterized for the first time. The results indicated that the metabolic pathways mainly include oxidation, reduction, methylation, and conjugation with glucuronide, taurine, glucose, and glutathione groups. This study provides a practical strategy for rapidly screening and identifying metabolites, and the results provide basic data for future pharmacological and toxicology studies of Schisantherin A and other lignin ingredients.

The dried roots of Euphorbia kansui S.L.Liou ex S.B.Ho have long been used to treat edema in China. However, the severe toxicity caused by Euphorbia kansui (EK) has seriously restricted its clinical application. Although EK was processed with vinegar to reduce its toxicity, the detailed mechanisms of attenuation in toxicity of EK stir-fried with vinegar (VEK) have not been well delineated. Diterpenoids are the main toxic ingredients of EK, and changes in these after processing may be the underlying mechanism of toxicity attenuation of VEK. 3-O-(2′E,4′Z-decadienoyl)-20-O-acetylingenol (3-O-EZ) is one of the diterpenoids derived from EK, and the content of 3-O-EZ was significantly reduced after processing. This study aims to explore the underlying mechanisms of toxicity reduction of VEK based on the change of 3-O-EZ after processing with vinegar. Based on the chemical structure of 3-O-EZ and the method of processing with vinegar, simulation experiments were carried out to confirm the presence of the product both in EK and VEK and to enrich the product. Then, the difference of peak area of 3-O-EZ and its hydrolysate in EK and VEK were detected by ultra-high-performance liquid chromatography (UPLC). Furthermore, the toxicity effect of 3-O-EZ and its hydrolysate, as well as the underlying mechanism, on zebrafish embryos were investigated. The findings showed that the diterpenoids (3-O-EZ) in EK can convert into less toxic ingenol in VEK after processing with vinegar; meanwhile, the content of ingenol in VEK was higher than that of EK. More interestingly, the ingenol exhibited less toxicity (acute toxicity, developmental toxicity and organic toxicity) than that of 3-O-EZ, and 3-O-EZ could increase malondialdehyde (MDA) content and reduce glutathione (GSH) content; cause embryo oxidative damage by inhibition of the succinate dehydrogenase (SDH) and superoxide dismutase (SOD) activity; and induce inflammation and apoptosis by elevation of IL-2 and IL-8 contents and activation of the caspase-3 and caspase-9 activity. Thus, this study contributes to our understanding of the mechanism of attenuation in toxicity of VEK, and provides the possibility of safe and rational use of EK in clinics.

Soy sauce contains a series of biogenic amines (BAs) which is a kind of bioactive organics relating to food quality and safety. High concentration of BAs may lead to remarkable physiological and toxicological influences on human bodies, including hypotension, dizziness, and headaches. Here, we systematically compared the levels of ten main BAs among 53 Chinese commercial soy sauces using an improved high-performance liquid chromatography (HPLC) method. The results showed that the brands and production regions were both important factors accounting for the BAs’ content. The contents of Cad, Spm, Try, Phe, His, and Tyr in dark soy sauces were higher than those in light soy sauces. His and Phe in dark soy sauces were 3.7 and 1.84 times higher than in light samples, respectively. Besides, it was surprising that the content of BAs in soy sauces hugely varied from place to place. This work comprehensively compared the content of BAs in soy sauces, showing the relation between soy sauce processes and BAs, offering abundant information for further research on BAs control.

Chemical research of the medicinal plant Hemsleya amabilis (Cucurbitaceae) yielded five new cucurbitane-type triterpenes hemslelis A–E (1–5) by silica gel column, ODS column, and semi-HPLC techniques. Their structures were determined by spectroscopic analysis and examined alongside existing data from prior studies. Compounds 1–5 were evaluated for their cytotoxic activities against three human tumor cell lines, Hela, HCT-8, and HepG-2, with the IC50 ranging from 5.9 to 33.9 μM compared to Cisplatin.

Gx-50 is a bioactive compound for the treatment of Alzheimer’s disease (AD) found in Sichuan pepper (Zanthoxylum bungeanum). In order to find a stronger anti-AD lead compound, 20 gx-50 (1–20) analogs have been designed and synthesized, and their molecular structures were determined based on nuclear magnetic resonance (NMR) and mass spectrometry (MS) analysis, as well as comparison with literature data. Compounds 1–20 were evaluated for their anti-AD potential by using DPPH radical scavenging assay for considering their anti-oxidant activity, thioflavin T (ThT) fluorescence assay for considering the inhibitory or disaggregate potency of Aβ, and transgenic Drosophila model assay for evaluating their rescue effect on memory loss. Finally, compound 13 was determined as a promising anti-AD candidate.

Allantoinase (ALLase; EC 3.5.2.5) possesses a binuclear metal center in which two metal ions are bridged by a posttranslationally carbamylated lysine. ALLase acts as a key enzyme for the biogenesis and degradation of ureides by catalyzing the conversion of allantoin into allantoate. Biochemically, ALLase belongs to the cyclic amidohydrolase family, which also includes dihydropyrimidinase, dihydroorotase, hydantoinase (HYDase), and imidase. Previously, the crystal structure of ALLase from Escherichia coli K-12 (EcALLase-K12) was reported; however, the two active site loops crucial for substrate binding were not determined. This situation would limit further docking and protein engineering experiments. Here, we solved the crystal structure of E. coli BL21 ALLase (EcALLase-BL21) at a resolution of 2.07 Å (PDB ID 8HFD) to obtain more information for structural analyses. The structure has a classic TIM barrel fold. As compared with the previous work, the two missed active site loops in EcALLase-K12 were clearly determined in our structure of EcALLase-BL21. EcALLase-BL21 shared active site similarity with HYDase, an important biocatalyst for industrial production of semisynthetic penicillin and cephalosporins. Based on this structural comparison, we discussed the functional role of the two active site loops in EcALLase-BL21 to better understand the substrate/inhibitor binding mechanism for further biotechnological and pharmaceutical applications. [ABSTRACT FROM AUTHOR]

In this research, a new triterpenoid, tirucalla-8,24-diene-3β,11β-diol-7-one (1), and eupha-8,24-diene-3β,11β-diol-7-one (2), which was isolated from Euphorbia kansui for the first time, together with twelve other known compounds (3–14), were isolated from the ethyl acetate extract of Euphorbia kansui. Their structures were elucidated based on High resolution electrospray ionization mass spectrometry (HR-ESI-MS), Infrared Spectroscopy (IR), 1D and 2D Nuclear Magnetic Resonance (NMR) data. Both constituents 1 and 2 exhibited moderate cytotoxicity against colon cancer HCT-116, gastric cancer MKN-45 and breast cancer MCF-7.

In recent years, the hepatotoxicity of Polygoni Multiflora Radix (PMR) has attracted increased research interest. Some studies suggest that anthraquinone may be the main hepatotoxic component. Most of the relevant studies have focused on the mononuclear anthraquinone component rather than binuclear anthraquinones. The hepatotoxicity of dinuclear anthraquinone (dianthrone) was investigated in a cell-based model. Next, a method for the determination of six free and total dianthonones in PMR and PMR Praeparata (PMRP) was established using ultra-high-performance liquid chromatography triple quadrupole mass spectrometry (UPLC-QQQ-MS/MS), which was then used to analyze the collected samples. The data show that four binuclear anthraquinone compounds were hepatotoxic and may be potential toxicity indicators for the safety evaluation of PMR and PMRP. Herein, we provide a theoretical basis for the improvement of PMRP quality standards. [ABSTRACT FROM AUTHOR]

Penicitroamide (1), a new metabolite with a new framework, was isolated from the ethyl acetate extract of the PDB (Potato Dextrose Broth) medium of Penicillium sp. (NO. 24). The endophytic fungus Penicillium sp. (NO. 24) was obtained from the healthy leaves of Tapiscia sinensis Oliv. The structure of penicitroamide (1) features a bicyclo[3.2.1]octane core unit with a high degree of carbonylization (four carbonyl groups and one enol group). The chemical structure of penicitroamide (1) was elucidated by analysis of 1D-, 2D-NMR and MS data. In bioassays, penicitroamide (1) displayed antibacterial potency against two plant pathogens, Erwinia carotovora subsp. Carotovora (Jones) Bersey, et al. and Sclerotium rolfsii Sacc. with MIC50 at 45 and 50 μg/mL. Compound 1 also showed 60% lethality against brine shrimp at 10 μg/mL. Penicitroamide (1) exhibited no significant activity against A549, Caski, HepG2 and MCF-7 cells with IC50 > 50 μg/mL. Finally, the possible biosynthetic pathway of penicitroamide (1) was discussed.

Magnolia officinalis Rehd. et Wils. and Magnolia officinalis Rehd. et Wils. var. biloba Rehd. et Wils, as the legal botanical origins of Magnoliae Officinalis Cortex, are almost impossible to distinguish according to their appearance traits with respect to medicinal bark. The application of AFLP molecular markers for differentiating the two origins has not yet been successful. In this study, a combination of e-nose measurements, e-tongue measurements, and chemical analyses coupled with multiple-source data fusion was used to differentiate the two origins. Linear discriminant analysis (LDA) and quadratic discriminant analysis (QDA) were applied to compare the discrimination results. It was shown that the e-nose system presented a good discriminant ability with a low classification error for both LDA and QDA compared with e-tongue measurements and chemical analyses. In addition, the discriminating capacity of LDA for low-level fusion with original data, similar to a combined system, was superior or equal to that acquired individually with the three approaches. For mid-level fusion, the combination of different principals extracted by PCA and variables obtained on the basis of PLS-VIP exhibited an analogous discrimination ability for LDA (classification error 0.0%) and was significantly superior to QDA (classification error 1.67–3.33%). As a result, the combined e-nose, e-tongue, and chemical analysis approach proved to be a powerful tool for differentiating the two origins of Magnoliae Officinalis Cortex. [ABSTRACT FROM AUTHOR]

Rhynchanthus beesianus W. W. Smith, an edible, medicinal, and ornamental plant, is mainly cultivated in China and Myanmar. The essential oil (EO) from R. beesianus rhizome has been used as an aromatic stomachic in China. The chemical composition and biological activities of EO from R. beesianus rhizome were reported for the first time. Based on gas chromatography with flame ionization or mass selective detection (GC-FID/MS) results, the major constituents of EO were 1,8-cineole (47.6%), borneol (15.0%), methyleugenol (11.2%), and bornyl formate (7.6%). For bioactivities, EO showed a significant antibacterial activity against Staphylococcus aureus, Enterococcus faecalis, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa, and Proteus vulgaris with the diameter of the inhibition zone (DIZ) (8.66–10.56 mm), minimal inhibitory concentration (MIC) (3.13–6.25 mg/mL), and minimal bactericidal concentration (MBC) (6.25–12.5 mg/mL). Moreover, EO (128 μg/mL) significantly inhibited the production of proinflammatory mediators nitric oxide (NO) (92.73 ± 1.50%) and cytokines tumor necrosis factor-α (TNF-α) (20.29 ± 0.17%) and interleukin-6 (IL-6) (61.08 ± 0.13%) in lipopolysaccharide (LPS)-induced RAW264.7 macrophages without any cytotoxic effect. Moreover, EO exhibited significant acetylcholinesterase (AChE) inhibitory activity (the concentration of the sample that affords a 50% inhibition in the assay (IC50) = 1.03 ± 0.18 mg/mL) and moderate α-glucosidase inhibition effect (IC50 = 11.60 ± 0.25 mg/mL). Thus, the EO could be regarded as a bioactive natural product and has a high exploitation potential in the cosmetics and pharmaceutical industries. [ABSTRACT FROM AUTHOR]

The water-resistant characteristics of ultraviolet crosslinked polyethylene (UV-XLPE) are investigated specially for the dependence on the hydrophilicities of auxiliary crosslinkers, which is significant to develop high-voltage insulating cable materials. As auxiliary crosslinking agents of polyethylene, triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA), and N,N′-m-phenylenedimaleimide (HAV2) are individually adopted to prepared XLPE materials with the UV-initiation crosslinking technique, for the study of water-tree resistance through the accelerating aging experiments with water blade electrode. The stress–strain characteristics and dynamic viscoelastic properties of UV-XLPE are tested by the electronic tension machine and dynamic thermomechanical analyzer. Monte Carlo molecular simulation is used to calculate the interaction parameters and mixing energy of crosslinker/water binary systems to analyze the compatibility between water and crosslinker molecules. Water-tree experiments verify that XLPE-TAIC represents the highest ability to inhibit the growth of water-trees, while XLPE-HAV2 shows the lowest resistance to water-trees. The stress–strain and viscoelastic properties show that the concentration of molecular chains connecting the adjacent lamellae in amorphous phase of XLPE-HAV2 is significantly higher than that of XLPE-TAIC and XLPE-TMPTMA. The molecular simulation results demonstrate that TAIC/water and TMPTMA/water binary systems possess a higher hydrophilicity than that of HAV2/water, as manifested by their lower interaction parameters and mixing free energies. The auxiliary crosslinkers can not only increase the molecular density of amorphous polyethylene between lamellae to inhibit water-tree growth, but also prevent water molecules at insulation defects from agglomerating into micro-water beads by increasing the hydrophilicity of auxiliary crosslinkers, which will evidently reduce the damage of micro-water beads on the amorphous phase in UV-XLPE. The better compatibility of TAIC and water molecules is the dominant reason accounting for the excellent water resistance of XLPE-TAIC. [ABSTRACT FROM AUTHOR]

In order to inhibit the outward-migrations of photo-initiator molecules in the ultraviolet-initiated crosslinking process and simultaneously improve the crosslinking degree and dielectric properties of crosslinked polyethylene (XLPE) materials, we have specifically developed surface-modified-SiO2/XLPE nanocomposites with the silica nanofillers that have been functionalized through chemical surface modifications. With the sulfur-containing silanes and 3-mercaptopropyl trimethoxy silane (MPTMS), the functional monomers of auxiliary crosslinker triallyl isocyanurate (TAIC) have been successfully grafted on the silica surface through thiol–ene click chemistry reactions. The grafted functional groups are verified by molecular characterizations of Fourier transform infrared spectra and nuclear magnetic resonance hydrogen spectra. Scanning electronic microscopy (SEM) indicates that the functionalized silica nanoparticles have been filled into polyethylene matrix with remarkably increased dispersivity compared with the neat silica nanoparticles. Under ultraviolet (UV) irradiation, the high efficient crosslinking reactions of polyethylene molecules are facilitated by the auxiliary crosslinkers that have been grafted onto the surfaces of silica nanofillers in polyethylene matrix. With the UV-initiated crosslinking technique, the crosslinking degree, insulation performance, and space charge characteristics of SiO2/XLPE nanocomposites are investigated in comparison with the XLPE material. Due to the combined effects of the high dispersion of nanofillers and the polar-groups of TAIC grafted on the surfaces of SiO2 nanofillers, the functionlized-SiO2/XLPE nanocomposite with an appropriate filling content represents the most preferable crosslinking degree with multiple improvements in the space charge characteristics and direct current dielectric breakdown strength. Simultaneously employing nanodielectric technology and functional-group surface modification, this study promises a modification strategy for developing XLPE nanocomposites with high mechanical and dielectric performances. [ABSTRACT FROM AUTHOR]

Space charge characteristics of cross-linked polyethylene (XLPE) at elevated temperatures have been evidently improved by the graft modifications with ultraviolet (UV) initiation technique, which can be efficiently utilized in industrial cable manufactures. Maleic anhydride (MAH) of representative cyclic anhydride has been successfully grafted onto polyethylene molecules through UV irradiation process. Thermal stimulation currents and space charge characteristics at the elevated temperatures are coordinately analyzed to elucidate the trapping behavior of blocking charge injection and impeding carrier transport which is caused by grafting MAH. It is also verified from the first-principles calculations that the bound states as charge carrier traps can be introduced by grafting MAH onto polyethylene molecules. Compared with pure XLPE, the remarkably suppressed space charge accumulations at high temperatures have been achieved in XLPE-g-MAH. The polar groups on the grafted MAH can provide deep traps in XLPE-g-MAH, which will increase charge injection barrier by forming a charged layer of Coulomb-potential screening near electrodes and simultaneously reduce the electrical mobility of charge carriers by trap-carrier scattering, resulting in an appreciable suppression of space charge accumulations inside material. The exact consistence of experimental results with the quantum mechanics calculations demonstrates a promising routine for the modification strategy of grafting polar molecules with UV initiation technique in the development of high-voltage DC cable materials. [ABSTRACT FROM AUTHOR]

Water-tree resistances of styrene block copolymer/polypropylene (SEBS/PP) composites are investigated by characterizing crystallization structures in correlation with the dynamic mechanical properties to elucidate the micro-structure mechanism of improving insulation performances, in which the accelerated aging experiments of water trees are performed with water-knife electrodes. The water-tree morphology in spherulites, melt-crystallization characteristics and lamella structures of the composite materials are observed and analyzed by polarizing microscopy (PLM), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), respectively. Dynamic relaxation and stress-strain characteristics are specifically studied by means of a dynamic thermomechanical analyzer (DMA) and electronic tension machine, respectively. No water-tree aging occurs in both the highly crystalline PP and the noncrystalline SEBS elastomer, while the water trees arising in SEBS/PP composites still has a significantly lower size than that in low-density polyethylene (LDPE). Compared with LDPE, the PP matrix of the SEBS/PP composite represent a higher crystallinity with a larger crystallization size in consistence with its higher mechanical strength and lower dynamic relaxation loss. SEBS molecules agglomerate as a "island" phase, and PP molecules crystallize into thin and short lamellae in composites, leading to the blurred spherulite boundary and the appreciable slips between lamellae under external force. The high crystallinity of the PP matrix and the strong resistance to slips between lamellae in the SEBS/PP composite essentially account for the remarkable inhibition on water-tree growth. [ABSTRACT FROM AUTHOR]

In order to improve the mechanical and dielectric properties of radome cyanate, a synergistic reinforcement method is employed to develop a resin-based ternary-composite with high heat-resistance and preferable radar-band transmission, which is expected to be applied to fabricate radomes capable of resisting high temperature and strong electric field. According to copolymerization characteristics and self-curing mechanism, epoxy resin (EP) and bismaleimide (BMI) are employed as reinforcements mixed into a cyanate ester (CE) matrix to prepare CE/BMI/EP composites of a heat-resistant radome material by high-temperature viscous-flow blending methods under the catalysis of aluminum acetylpyruvate. The crystallization temperature, transition heat, and reaction rate of cured polymers were tested to analyze heat-resistance characteristics and evaluate material synthesis processes. Scanning electron microscopy was used to characterize the micro-morphology of tensile fracture, which was combined with the tensile strength test and dynamic thermomechanical analysis to investigate the composite modifications on tenacity and rigidity. Weibull statistics were performed to analyze the experimental results of the dielectric breakdown field, and the dielectric-polarization and wave-transmission performances were investigated according to alternative current dielectric spectra. Compared with the pure CE and the CE composites individually reinforced by EP or BMI, the CE/BMI/EP composite acquires the most significant amelioration in both the mechanical and electrical insulation performances as indicated by the breaking elongation and dielectric breakdown strength being simultaneously improved by 40%, which are consistently manifested by the obviously increased transverse lines uniformly distributed on the fracture cross-section. Furthermore, the glass-transition temperature of CE/BMI/EP composite reaches the highest values of nearly 300 °C, with the relative dielectric constant and dielectric loss being mostly reduced to less than 3.2 and 0.01, respectively. The experimental results demonstrate that the CE/BMI/EP composite is a highly-qualified wave-transmission material with preferences in mechanical, thermostability, and electrical insulation performances, suggesting its prospective applications in low-frequency transmittance radomes. [ABSTRACT FROM AUTHOR]

The yield and quality of goji (Lycium barbarum L.) fruit are heavily dependent on fertilizer, especially the availability of nitrogen, phosphorus, and potassium (N, P, and K, respectively). In this study, we performed a metabolomic analysis of the response of goji berry to nitrogen fertilizer levels using an Ultra Performance Liquid Chromatography–Electrospray Ionization–Tandem Mass Spectrometry (UPLC-ESI-MS/MS) method. There was no significant difference in the fruit yield or the commodity grade between N0 (42.5 g/plant), N1 (85 g/plant), and N2 (127.5 g/plant). The primary nutrients of the goji berry changed with an increasing nitrogen fertilization. Comparative metabolomic profiling of three nitrogen levels resulted in the identification of 612 metabolites, including amino acids, flavonoids, carbohydrates, organic acids, and lipids/alcohols, among others, of which 53 metabolites (lipids, fatty acids, organic acids, and phenolamides) demonstrated significant changes. These results provide new insights into the molecular mechanisms of the relationship between yield and quality of goji berry and nitrogen fertilizer. [ABSTRACT FROM AUTHOR]

The dried roots of Euphorbia kansui S.L.Liou ex S.B.Ho have long been used to treat edema in China. However, the severe toxicity caused by Euphorbia kansui (EK) has seriously restricted its clinical application. Although EK was processed with vinegar to reduce its toxicity, the detailed mechanisms of attenuation in toxicity of EK stir-fried with vinegar (VEK) have not been well delineated. Diterpenoids are the main toxic ingredients of EK, and changes in these after processing may be the underlying mechanism of toxicity attenuation of VEK. 3-O-(2′E,4′Z-decadienoyl)-20-O-acetylingenol (3-O-EZ) is one of the diterpenoids derived from EK, and the content of 3-O-EZ was significantly reduced after processing. This study aims to explore the underlying mechanisms of toxicity reduction of VEK based on the change of 3-O-EZ after processing with vinegar. Based on the chemical structure of 3-O-EZ and the method of processing with vinegar, simulation experiments were carried out to confirm the presence of the product both in EK and VEK and to enrich the product. Then, the difference of peak area of 3-O-EZ and its hydrolysate in EK and VEK were detected by ultra-high-performance liquid chromatography (UPLC). Furthermore, the toxicity effect of 3-O-EZ and its hydrolysate, as well as the underlying mechanism, on zebrafish embryos were investigated. The findings showed that the diterpenoids (3-O-EZ) in EK can convert into less toxic ingenol in VEK after processing with vinegar; meanwhile, the content of ingenol in VEK was higher than that of EK. More interestingly, the ingenol exhibited less toxicity (acute toxicity, developmental toxicity and organic toxicity) than that of 3-O-EZ, and 3-O-EZ could increase malondialdehyde (MDA) content and reduce glutathione (GSH) content; cause embryo oxidative damage by inhibition of the succinate dehydrogenase (SDH) and superoxide dismutase (SOD) activity; and induce inflammation and apoptosis by elevation of IL-2 and IL-8 contents and activation of the caspase-3 and caspase-9 activity. Thus, this study contributes to our understanding of the mechanism of attenuation in toxicity of VEK, and provides the possibility of safe and rational use of EK in clinics. [ABSTRACT FROM AUTHOR]

Gx-50 is a bioactive compound for the treatment of Alzheimer's disease (AD) found in Sichuan pepper (Zanthoxylum bungeanum). In order to find a stronger anti-AD lead compound, 20 gx-50 (1–20) analogs have been designed and synthesized, and their molecular structures were determined based on nuclear magnetic resonance (NMR) and mass spectrometry (MS) analysis, as well as comparison with literature data. Compounds 1–20 were evaluated for their anti-AD potential by using DPPH radical scavenging assay for considering their anti-oxidant activity, thioflavin T (ThT) fluorescence assay for considering the inhibitory or disaggregate potency of Aβ, and transgenic Drosophila model assay for evaluating their rescue effect on memory loss. Finally, compound 13 was determined as a promising anti-AD candidate. [ABSTRACT FROM AUTHOR]

Since the cost of Ophiocordyceps sinensis, an important fungal drug used in Chinese medicine, has increased dramatically, and the counterfeits may have adverse health effects, a rapid and precise marker using the peptide mass spectrometry identification system could significantly enhance the regulatory capacity. In this study, we determined the marker peptides in the digested mixtures of fungal proteins in wild O. sinensis fruiting bodies and various commercially available mycelium fermented powders using ultra-performance liquid chromatography/Orbitrap Fusion mass spectrometry coupled with chemometrics. The results indicated the following marker peptides: TLLEAIDSIEPPK (m/z 713.39) was identified in the wild O. sinensis fruiting body, AVLSDAITLVR (m/z 579.34) was detected in the fermented O. sinensis mycelium powder, FAELLEK (m/z 849.47) was found in the fermented Ophiocordyceps mycelium powder, LESVVTSFTK (m/z 555.80) was discovered in the artificial Ophiocordyceps mycelium powder, and VPSSAVLR (m/z 414.75) was observed in O. mortierella mycelium powder. In order to verify the specificity and applicability of the method, the five marker peptides were synthesized and tested on all samples. All in all, to the best of our knowledge, this is the first time that mass spectrometry has been employed to detect the marker peptides of O.sinensis and its related products. [ABSTRACT FROM AUTHOR]

Plant secondary metabolites (SMs) are not only a useful array of natural products but also an important part of plant defense system against pathogenic attacks and environmental stresses. With remarkable biological activities, plant SMs are increasingly used as medicine ingredients and food additives for therapeutic, aromatic and culinary purposes. Various genetic, ontogenic, morphogenetic and environmental factors can influence the biosynthesis and accumulation of SMs. According to the literature reports, for example, SMs accumulation is strongly dependent on a variety of environmental factors such as light, temperature, soil water, soil fertility and salinity, and for most plants, a change in an individual factor may alter the content of SMs even if other factors remain constant. Here, we review with emphasis how each of single factors to affect the accumulation of plant secondary metabolites, and conduct a comparative analysis of relevant natural products in the stressed and unstressed plants. Expectantly, this documentary review will outline a general picture of environmental factors responsible for fluctuation in plant SMs, provide a practical way to obtain consistent quality and high quantity of bioactive compounds in vegetation, and present some suggestions for future research and development. [ABSTRACT FROM AUTHOR]