Doping and defects in carbon nitride cause efficient in situ H2O2 synthesis to allow efficient photocatalytic sterilization.

In situ photocatalytic synthesis of H2O2 for disinfection has attracted widespread attention because it is a clean and environmentally friendly sterilization method. Graphitic carbon nitride has been used as a very selective photocatalyst for H2O2 generation but has some limitations (e.g., insufficient light absorption, rapid electron-hole recombination, and slow direct two-electron reduction processes) that prevent efficient H2O2 production. In this study, potassium-doped graphite carbon nitride with nitrogen vacancies (NDKCN) was prepared using a simple method involving a thermal fusion salt and N2 calcination, which possessed an ultrathin nanosheet structure (1.265 nm) providing abundant active sites. Synergistic effects caused by nitrogen vacancies and K+ and I- doping in the NDKCN photocatalyst gave the NDKCN a good ability to absorb light, undergo fast charge transfer, and give a high photoelectric current response. The optimized photocatalytic H2O2 yield of the NDKCN was 780.1 µM·g-1·min-1, which was 10 times the yield of the pristine g-C3N4. Tests involving quenching reactive species, electron spin resonance, and rotating disk electrodes indicated that one-step two-electron direct reduction on the NDKCN caused excellent H2O2 generation performance. The ability to efficiently generate H2O2 in situ gave NDKCN an excellent bactericidal performance, and 7.3 log10 (colony-forming units·mL-1) of Escherichia coli were completely eliminated within 80 min. Scanning electron microscopy images before and after sterilization indicated the changes in bacteria caused by the catalytic activity. The new g-C3N4-based photocatalyst and similar rationally designed photocatalysts with doping and defects offer efficient and simple in situ H2O2 sterilization.

Electronic structure regulation of Fe single atom coordinated nitrogen doping MoS2 catalyst enhances the Fenton-like reaction efficient for organic pollutant control.

An efficient cathode for a Fenton-like reaction based on hydrogen peroxide (H2O2) has significant implications for the potential application of the advanced oxidation process. However, the low H2O2 selectivity and efficient activation remain challenging in wastewater treatment. In the present study, a single Fe atom doped, nitrogen-coordinated molybdenum disulfide (Fe1/N/MoS2) cathode that exhibited asymmetric wettability and self-absorption molecular oxygen was successfully prepared for pollutant degradation. The X-ray absorption near-edge structure and extended X-ray absorption fine structure of Fe1N3 in the Fe1/N/MoS2 catalyst were determined. The electronic structure demonstrated favorable H2O2 selectivity (75%) in a neutral solution and the cumulative hydroxyl radical concentration was 14 times higher than the pure carbon felt. After 10 consecutive reaction experiments, the removal ratio of paracetamol still reached 97%, and the catalytic performance did not decrease significantly. This work deeply understands the catalytic mechanism of Fenton-like reaction between single Fe atom and MoS2 double reaction sites, and proves that the regulation of the electronic structure of Fe single atom is an effective strategy to improve the activity of Fenton-like reaction.

Mo-Based Heterogeneous Interface and Sulfur Vacancy Synergistic Effect Enhances the Fenton-like Catalytic Performance for Organic Pollutant Degradation.

Heterogeneous Fenton-like reactions (HFLRs) based on the in situ electrochemical generation of hydrogen peroxide (H2O2) are one of the green methods to remediate organic pollutants in wastewater. However, the design of Fenton-like catalysts with specific active sites and high pollutant degradation rate is still challenging. Here, MoS2-MoC and MoS2-Mo2N catalytic cathodes with heterojunctions were successfully prepared, and the mechanism by which hydroxyl radicals and singlet oxygen (1O2) were generated cleanly without adding chemical additives other than oxygen was clarified. The composite catalysts contained more sulfur vacancies, and the catalytic cathode achieved a high paracetamol pollutant degradation efficiency with 0.17 kWh g-1 TOC specific energy consumption. And almost 5 times higher activity was achieved compared to a pure MoS2 catalytic cathode. Experimental studies confirmed that the production of 1O2 was based on the transformation of superoxide radicals by Mo6+, and 1O2 accounted for approximately 66% of the total degradation and enhanced the nonradical behavior in the reaction. This work provides a sustainable strategy for pollutant utilization, which is valuable for solving the difficult problems of HFLRs and developing new environmental remediation technologies.

Catalysts containing Fe and Mn from dewatered sludge showing enhanced electrocatalytic degradation of triclosan.

The present work demonstrates a simple one-step pyrolysis method for the synthesis of a catalytic sludge-based carbon (SBC) biochar containing Fe and Mn from dehydrated sludge with added KMnO4 and Fe(II). The electrocatalytic degradation of triclosan (TCS) in water was evaluated using an Fe/Mn-SBC cathode to promote a heterogeneous Fenton-like reaction. The catalyst generated at 500 °C exhibited an abundant porous structure and a relatively high surface area, and produced an electrode with better conductivity and electron diffusion. The presence of metal oxides changed the surface structure defects of this biochar and enhanced its catalytic performance while increasing the electrochemically active surface area by 72.68 mF/cm2 compared with plain SBC. TCS was degraded (91.3%) within 180 min by oxygen species generated in situ on an Fe/Mn-SBC cathode because the activation energy for oxygen reduction was lowered by 4.62 kJ/mol. The degradation of TCS followed pseudo first-order kinetics and was controlled by TCS diffusion and interfacial chemical reactions between adsorbed TCS and the electrode. Possible TCS degradation pathways were devised based on the main intermediates, and 1O2 was found to be more important than •OH radicals. Through toxicity test and prediction, the toxicity of degradation was gradually reduced. This study demonstrates a simple and ecofriendly method for the electrocatalytic degradation of organic pollutants.

Methionine enkephalin inhibits colorectal cancer by remodeling the immune status of the tumor microenvironment.

There is evidence that methionine enkephalin (MENK), an opioid peptide, promotes anti-tumor immune responses. In this study, the effect of MENK on colorectal cancer (CRC) and its mechanisms of action were examined in vivo. The intraperitoneal administration of 20 mg/kg MENK effectively inhibited MC38 subcutaneous colorectal tumor growth in mice. MENK inhibited tumor progression by increasing the immunogenicity and recognition of MC38 cells. MENK down-regulated the oncogene Kras and anti-apoptotic Bclxl and Bcl2, suppressed Il1b, Il6, iNOS, and Arg1 (encoding inflammatory cytokines), and increased Il17a and Il10 levels. MENK promoted a tumor suppressive state by decreasing the immune checkpoints Pd-1, Pd-l1, Lag3, Flgl1, and 2b4 in CRC. MENK also altered the immune status of the tumor immune microenvironment (TIME). It increased the infiltration of M1-type macrophages, CD8+T cells, and CD4+T cells and decreased the proportions of G-MDSCs, M-MDSCs, and M2-type macrophages. MENK accelerated CD4+TEM and CD8+TEM cell activation in the TIME and up-regulated IFN-γ, TNF-α, and IL-17A in CD4+T cells and Granzyme B in CD8+T cells. In addition, analyses of PD-1 and PD-L1 expression indicated that MENK promoted the anti-tumor immune response mediated by effector T cells. Finally, OGFr was up-regulated at the protein and mRNA levels by MENK, and the inhibitory effects of MENK on tumor growth were blocked by NTX, a specific blocker of OGFr. These finding indicate that MENK remodels the TIME in CRC to inhibit tumor progression by binding to OGFr. MENK is a potential therapeutic agent for CRC, especially for improving the efficacy of immunotherapy.

Stepwise dechlorination of chlorinated alkenes on an Fe-Ni/rGO/Ni foam cathode: Product control by one-electron-transfer reactions.

Research on the stepwise hydrogenation dechlorination of chlorinated alkenes forms an important basis for eliminating toxic intermediate incomplete dechlorination products. The low-cost Fe-Ni/rGO/Ni foam cathode both supplied electrons and exhibited hydrogen conversion activity, and it was an excellent tool for the study of stepwise dechlorination. Electrochemical reduction experiments were carried out on homologous chlorinated alkenes. The conditions affecting the dechlorination efficiency and the repeatability of the catalytic electrode were analyzed. The trichloroethylene (TCE) removal rates were all above 78.0% over 8 cycles. The maximum EHDC efficiency was as high as 86.1%, and the faradaic efficiency was over 78.8%. Electrochemical methods combined with the calculation of the electron transfer number are proposed to verify the good hydrogenation ability of the electrode and the stepwise reduction ability at proper voltages. The stepwise dechlorination electroreduction characteristics of chlorinated alkenes were explained. The C-Cl bond dissociation enthalpies of chlorinated alkenes were calculated by density functional theory (DFT), and the 4-Cl and 5-Cl of TCE were expected to be removed first. The stepwise cleavage of chlorinated alkenes on Fe-Ni/rGO/Ni foam during dichlorination provided a reference for controlling the reduction products of chlorinated alkenes and preventing the pollution caused by toxic intermediate products formed during incomplete dechlorination.

Lanicepines A and B, Sesquiterpenes with Amino Acid-Derived Substituents from the Flowering Aerial Parts of Saussurea laniceps.

Two new guaianolide sesquiterpenes, lanicepines A (1) and B (2), possessing unusual amino acid-derived substituents at C-13, were isolated from the flowering aerial parts of Saussurea laniceps, a traditional herbal medicine also known as "snow lotus". The structures of 1 and 2 were elucidated based on spectroscopic analysis including applications of the modified Mosher's method and Marfey's method as well as ECD calculations. Lanicepine A (1) contains a dihydropyridinone moiety with a carbamoyl and a hydroxymethyl group. This substituent was considered to consist of asparagine and a C4 unit. In contrast, lanicepine B (2) has a substituent that seems to be derived from l-proline and a C4 unit. Lanicepines A (1) and B (2) and two related known sesquiterpenes isolated from the same plant material, 11ß,13-dihydrodesacylcynaropicrin (3) and 11ß,13-dihydrodesacylcynaropicrin 8-O-ß-d-glucoside (4), demonstrated inhibitory activity against IL-1ß production from LPS-stimulated microglial cells.

Sesquiterpene lactones from Carpesium abrotanoides L. and their activity in inducing protective autophagy.

Fourteen sesquiterpene lactones were isolated from the whole plant of Carpesium abrotanoides L. Their structures were determined on the basis of comprehensive spectroscopic data analysis. All compounds were screened for their cytotoxic activity, and compound 6 showed the strongest activity (IC50 2.73 - 7.21 µM) against five human cancer cell lines, including A549, HepG2, HCT116, MDA-MB-231, and CNE2. Compound 6 was further investigated. Compound 6 effectively induced G2/M cell cycle arrest and ROS accumulation in a dose-dependent manner, which further led to apoptosis in cancer cells. Interestingly, compounds 1 and 6 could also activate protective autophagy, which was reported for the first time in sesquiterpene isolated from Carpesium abrotanoides. In addition, compounds 1 and 6 could induce lysosomal biogenesis by 173.2% and 163.7%, respectively. In sum, sesquiterpene lactones from Carpesium abrotanoides could induce apoptosis and protective autophagy in cancer cells, which provide a serial of compounds with potential clinical applications.

Tagitinin C induces ferroptosis through PERK-Nrf2-HO-1 signaling pathway in colorectal cancer cells.

Rationale: Colorectal cancer (CRC) is a common malignant tumor of the digestive system. However, the efficacy of surgery and chemotherapy is limited. Ferroptosis is an iron- and reactive oxygen species (ROS)-dependent form of regulated cell death (RCD) and plays a vital role in tumor suppression. Ferroptosis inducing agents have been studied extensively as a novel promising way to fight against therapy resistant cancers. The aim of this study is to investigate the mechanism of action of tagitinin C (TC), a natural product, as a novel ferroptosis inducer in tumor suppression. Methods: The response of CRC cells to tagitinin C was assessed by cell viability assay, clonogenic assay, transwell migration assay, cell cycle assay and apoptosis assay. Molecular approaches including Western blot, RNA sequencing, quantitative real-time PCR and immunofluorescence were employed as well. Results: Tagitinin C, a sesquiterpene lactone isolated from Tithonia diversifolia, inhibits the growth of colorectal cancer cells including HCT116 cells, and induced an oxidative cellular microenvironment resulting in ferroptosis of HCT116 cells. Tagitinin C-induced ferroptosis was accompanied with the attenuation of glutathione (GSH) levels and increased in lipid peroxidation. Mechanistically, tagitinin C induced endoplasmic reticulum (ER) stress and oxidative stress, thus activating nuclear translocation of nuclear factor erythroid 2-related factor 2 (Nrf2). As a downstream gene (effector) of Nrf2, heme oxygenase-1 (HO-1) expression increased significantly with the treatment of tagitinin C. Upregulated HO-1 led to the increase in the labile iron pool, which promoted lipid peroxidation, meanwhile tagitinin C showed synergistic anti-tumor effect together with erastin. Conclusion: In summary, we provided the evidence that tagitinin C induces ferroptosis in colorectal cancer cells and has synergistic effect together with erastin. Mechanistically, tagitinin C induces ferroptosis through ER stress-mediated activation of PERK-Nrf2-HO-1 signaling pathway. Tagitinin C, identified as a novel ferroptosis inducer, may be effective chemosensitizer that can expand the efficacy and range of chemotherapeutic agents.

Ten new nortriterpenes from Euphorbia resinifera and their anti-tomato yellow leaf curl virus activities.

Ten new nortriterpenes, euphorbiumrins A-J (1-10), together with three known analogues (11-13) were isolated from the latex of Euphorbia resinifera. Their structures were established on the basis of extensive spectroscopic analyses (IR, UV, HRESIMS, 1D and 2D NMR). Their inhibitions on tomato yellow leaf curl virus (TYLCV) were evaluated and compound 5 exhibited significant anti-TYLCV activity with an inhibition rate of 71.7% at concentration of 40 µg/mL.

Revealing the Structure Evolution of Heterogeneous Pd Catalyst in Suzuki Reaction via the Identical Location Transmission Electron Microscopy.

The mechanism of palladium nanoparticles (Pd NPs)-catalyzed cross-coupling reactions has been the subject of intense debate since the recognition of catalytic active sites involving a wide array of dynamic changed Pd species. Here, through the combination of the hot filtration experiment together with the recently developed identical location transmission electron microscopy (IL-TEM) method, the delicate structure evolution of highly dispersed Pd NPs supported on oxygen-functionalized carbon nanotubes (Pd/oCNTs) as well as the kinetics properties of derived dissolved species in liquid phase were systemically investigated in the Suzuki-Miyaura reaction. The result indicates that the leached Pd components caused by the strong adsorption of reactants might have a significant contribution to the coupling products, and the degree for different substrates follows the order of iodobenzene > phenylboronic acid > bromobenzene. Meanwhile, the typical three sequential behaviors of supported Pd NPs, including dissolution, deposition, and growth, along with the increase of the conversion throughout the reaction were spatiotemporally observed by tracking the evolution of individually identifiable NPs. The performed work not only provides direct evidence for the interaction between Pd NPs surface with reactants on atomic scale but also gives a valuable reference for fundamentally understanding the mechanism of the heterogeneous Pd-catalyzed Suzuki coupling process as well as rational design of next-generation catalysts with high efficiency and reusability for synthetic applications.

Tagitinin A from Tithonia diversifolia provides resistance to tomato spotted wilt orthotospovirus by inducing systemic resistance.

Tomato spotted wilt orthotospovirus (TSWV) causes devastating losses to agronomic and ornamental crops worldwide. Currently, there is no effective strategy to control this disease. Use of biotic inducers to enhance plant resistance to viruses maybe an effective approach. Our previous study indicated that Tagitinin A (Tag A) has a high curative and protective effect against TSWV. However, the underlying molecular mechanism of Tag A-mediated antiviral activity remains unknown. In this study, Tag A reduced the expression of the NSs, NSm genes was very low in untreated leaves following TSWV infection. In addition, the expression of all TSWV genes in the inoculated and systemic leaves was inhibited in the protective assay, and with an inhibition rate of more than 85% in systemic leaves. Tag A increased phenylalanine ammonia-lyase (PAL) activity in the curative and protective assays. The concentrations of jasmonic acid (JA) and jasmonic acid -isoleucine (JA-Ile) and the expression of its key gene NtCOI1 in Tag A-treated and systemic leaves of treated plants were significantly higher than those of the control plant. Furthermore, Tag A-induced resistance to TSWV could be eliminated by VIGS-mediated silencing of the NtCOI1 gene. These indicated that Tag A acts against TSWV by activating the JA defense signaling pathway.

Diterpenes with potential treatment of vitiligo from the aerials parts of Euphorbia antiquorum L.

Six new diterpenes Euphonoids A-F including one ingenol (1), three lathyrane (2-5), one ent-abietane (6) and fifteen known derivatives (7-21) were isolated from the aerial parts of Euphorbia antiquorum L. Their structures were elucidated by physical data analysis. Compounds 1, 12, and 16 improve the melanogenesis in B16 cells in vitro.

Two New C21 Steroidal Glycosides from the Roots of Cynanchum paniculatum.

Two new C21 steroidal glycosides, paniculatumosides H and I, together with four known ones were isolated from the roots of Cynanchum paniculatum (Bge.) Kitag. Their structures were identified by spectroscopic methods including extensive 1D and 2D NMR techniques. All compounds were subjected to detect the anti-tobacco mosaic virus (TMV) activities and their cytotoxities against three human tumor cell lines (SMMC-7721, MDA-MB-231 and A549). The results showed that compounds 1 and 5 exhibited potent protective activities against TMV, while 2, 4 and 6 had moderate effects on the SMMC-7721 cancer cells viability.

Diterpenoid compounds from Wedelia trilobata induce resistance to Tomato spotted wilt virus via the JA signal pathway in tobacco plants.

Tomato spotted wilt virus (TSWV) causes major losses of many crops worldwide. Several strategies have been attempted to control disease caused by TSWV. However, many challenges for the effective control of this disease remain. A promising approach is the use of abiotic or biotic inducers to enhance plant resistance to pathogens. We screened a diterpenoid compound from Wedelia trilobata, 3α-Angeloyloxy-9ß-hydroxy-ent-kaur-16-en-19-oic acid (AHK), which had higher curative and protective effects against TSWV than the ningnanmycin control. The rapid initiation of the expression of all the TSWV genes was delayed by more than 1d in the curative assay, and the expression of the NSs, NSm and RdRp genes was inhibited. In addition, the replication of all TSWV genes in systemic leaves was inhibited in the protective assay, with an inhibition rate of more than 90%. The concentrations of jasmonic acid (JA) and jasmonic acid isoleucine (JA-ILE) in the AHK-treated and systemic leaves of the treated plants were significantly higher than those observed in the control. The results suggested that AHK can induce systemic resistance in treated plants. The transcription of the NtCOI1 gene, a key gene in the JA pathway, was significantly higher in both the inoculated and systemic leaves of the AHK-treated plants compared to the control. The AHK-induced resistance to TSWV in Nicotiana benthamiana could be eliminated by VIGS-mediated silencing of the NtCOI1 gene. These results indicated that AHK can activate the JA pathway and induce systemic resistance to TSWV infection.

Anti-TMV Effects of Amaryllidaceae Alkaloids Isolated from the Bulbs of Lycoris radiata and Lycoricidine Derivatives.

Fifteen known amaryllidaceae alkaloids were isolated from the bulbs of Lycoris radiata. Some of the compounds and lycoricidine derivatives had been screened for the activities against tobacco mosaic virus (TMV) by the conventional half-leaf method. Lycoricidine derivatives were also carried out the assay of effect on systemic infection of TMV by western-blot and RT-PCR analysis. The tested compounds showed moderate inactivation effect, whereas the lycoricidine derivatives showed good protective effect. The protective inhibitory activity of compounds L1 (N-methyl-2,3,4-trimethoxylycoricidine) (60.8%) and L3 (N-methyl-2-methoxy-3,4-acetonidelycoricidine) (62.0%) was almost similar to the positive control, Ningnanmycin (66.4%). RT-PCR and Western-blot analysis displayed that compounds L1, L3, L5 (N-allyl-2,3,4-triallyloxylycoricidine) exhibited antiviral activity, which was evidenced by reducing TMV-CP gene replication and TMV-CP protein expression. Additionally, defensive enzyme activities confirmed that compound L1 could increase the activity of PAL, POD, SOD to improve disease resistance of tobacco.

Cytotoxic indole alkaloids from Melodinus khasianus and Melodinus tenuicaudatus.

Four new indole alkaloids, melodinusines A-D (1, 2, 6, and 7), along with 26 known indole alkaloids, were isolated from Melodinus tenuicaudatus and Melodinus khasianus (Melodinus genus). Among them, 1 and 2 are aspidospermine-aspidospermine-type bisindole alkaloids while 7 is a novel melodinus-type alkaloid. Their structures were established on the basis of comprehensive spectroscopic data analysis and the structure of 7 was further confirmed by single-crystal X-ray diffraction analysis. Their cytotoxic activities against five human cancer cell lines, HL-60, SMMC-7721, A-549, MCF-7, and SW480 were also evaluated.

Identification of Ingol and Rhamnofolane Diterpenoids from Euphorbia resinifera and Their Abilities to Induce Lysosomal Biosynthesis.

The phytochemical study of Euphorbia resinifera afforded 18 structurally diverse diterpenoids, including 14 new ingol-type diterpenoids, euphorblins A-N (1-14), a new rhamnofolane diterpenoid, euphorblin O (15), and three known analogues (16-18). The structures of these compounds were deduced using 2D NMR spectroscopy and NOE experiments. The structure of compound 1 was confirmed by single-crystal X-ray crystallography. The abilities of the compounds to enhance lysosomal biosynthesis were evaluated through LysoTracker Red staining. Among the 10 active compounds, compounds 2, 4, and 18 showed remarkable immunofluorescence strength, and their LysoTracker staining intensities were 155.9%, 143.5%, and 140.7%, respectively, greater than that of the control. A series of lysosomal genes were also found to be upregulated by these compounds, which further confirms their ability to induce lysosome biosynthesis and suggests that these diterpenoids have potential as lead compounds for the development of drugs for the treatment of lysosome-related diseases.

Rigenolides D-H, norsecoiridoid and secoiridoids from Gentiana rigescens Franch.

Five new compounds, rigenolides D-H (1-5), were isolated from the aerial parts of Gentiana rigescens Franch. Their structures were assigned by detailed spectroscopic analyses and chemical conversions. Rigenolides D (1) and E (2) were elucidated to be a secoiridoid and a norsecoiridoid, respectively, possessing a dienone moiety in common. Rigenolides F-H (3-5) were assigned as acylated secoiridoid glucosides.

Two novel diterpenoid heterodimers, Bisebracteolasins A and B, from Euphorbia ebracteolata Hayata, and the cancer chemotherapeutic potential of Bisebracteolasin A.

Rare ent-abietane-rosane diterpenoid heterodimers, Bisebracteolasins A and B (1 and 2, respectively), were isolated from the roots of Euphorbia ebracteolata Hayata. Their structures and absolute configurations were elucidated from spectroscopic data and X-ray diffraction analysis. Compounds 1 and 2 exhibited moderate cytotoxic effects against five cancer cell lines. Compound 1 showed more effective antiproliferative activities against human tumour cells, HL-60 and SMMC-7721, with IC50 values of 2.61 and 4.08 µM, respectively, than 2. Both compounds 1 and 2 inhibit the colorectal cancer stem cell line P6C with IC50 values of 16.48 and 34.76 µM, respectively. Moreover, preliminary biological tests showed compound 1 exhibited inhibitory activity towards tumoursphere formation and migration of the P6C cell line. Overall, we identified two novel diterpenoid heterodimers, and Bisebracteolasin A exhibits therapeutic potential in impeding tumour growth and metastatic ability of cancer stem cells.