Role of iron oxide in retarding the graphitization of de-oiled asphaltenes for amorphous carbon.

The solvent deasphalting (SDA) process is widely recognized as a significant technology in processing inferior oil. However, de-oiled asphaltene (DOA), which accounts for about 30% of feedstocks, is not well utilized in conventional processing methods to date. Considering its complicated structure and high heteroatom and metal contents, DOA is suitable for preparing amorphous carbon. Herein, we obtained amorphous carbon from inferior de-oiled asphaltene through direct carbonization of a mixture of DOA and Fe2O3 and revealed the mechanism of iron oxide in retarding graphitization to increase the disordered structure content. After the addition of Fe2O3, XRD results showed that the content of amorphous carbon increased from 25.57% to 59.48%, and a higher defect degree could also be observed in Raman spectra, thus resulting in better electrochemical performance in Na-ion half-cells. As a coke core, Fe2O3 could accelerate the polycondensation of asphaltene molecules; meanwhile, oxygen species derived from Fe2O3 could capture excess H free radicals in the initial pyrolysis stage, which inhibited the formation of planar polycyclic aromatic molecules and weakened π-π interactions. Moreover, O atoms could embed into the carbon skeleton by reacting with DOA at higher temperatures, which could further twist and break the intact carbon layer. Both of the factors enhanced the proportion of amorphous carbon. This work not only provides a new understanding of controlling the carbonization process, but it also promotes the development of the SDA process.

Controllable Synthesis of N- and O-Containing Heterocycles via Formal [3 + 2] and [5 + 2] Cyclizations.

The controllable synthesis of spirooxindole-dihydrofurans and spirooxindole-benzazepines was developed through formal [3 + 2] and [5 + 2] cyclization reactions from 2-(2-oxoindolin-3-yl)malononitriles and ortho-aminobenzaldehydes, respectively. A variety of spirooxindole-benzazepines were facilely constructed via a furan ring-open-involved hydride transfer/cyclization process. It is noteworthy that the application of the hydride-transfer-involved [5 + 2] cyclization strategy for construction of spirobenzazepines was unprecedented. In addition, the spiro N- and O-containing heterocycles were highly functionalized by amino, amide, and cyano groups, which were conducive to late-stage functionalization.

Study on the Performance of Ni-MoS2 Catalysts with Different MoS2 Structures for Dibenzothiophene Hydrodesulfurization.

Hydrodesulfurization (HDS) is an important process for the production of clean fuel oil, and the development of a new environmentally friendly, low-cost sulfided catalyst is key research in hydrogenation technology. Herein, commercial bulk MoS2 and NiCO3·2NiOH2·4H2O were first hydrothermally treated and then calcined in a H2 or N2 atmosphere to obtain Ni-MoS2 HDS catalysts with different structures. Mechanisms of hydrothermal treatment and calcination on Ni-MoS2 catalyst structures were investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), electron paramagnetic resonance (EPR), and X-ray photoelectron spectroscopy (XPS). The catalytic performance of Ni-MoS2 catalysts was evaluated by the HDS reaction of dibenzothiophene (DBT) on a fixed bed reactor, and the structure-activity relationship between the structures of the Ni-MoS2 catalyst and the HDS of DBT was discussed. The results showed that the lateral size, the number of stacked layers, and the S/Mo atomic ratio of MoS2 in the catalyst decreased and then increased with the increase of the hydrothermal treatment temperature, reaching the minimum at the hydrothermal treatment temperature of 150 °C, i.e., the lateral size of MoS2 in the catalyst was 20-36 nm, the number of stacked layers of MoS2 was 5.4, and the S/Mo ratio in the catalyst was 1.80. In addition, the effects of different calcination temperatures and calcination atmospheres on the catalyst structures were investigated at the optimum hydrothermal treatment temperature. The Ni-Mo-S and NixSy ratios of the catalysts increased and then decreased with the increasing calcination temperature under a H2 atmosphere, reaching a maximum at a calcination temperature of 400 °C. Therefore, DBT exhibited the best HDS activity over the H-NiMo-150-400 catalyst, and the desulfurization rate of DBT reached 94.7% at a reaction temperature of 320 °C.

1H-NMR-Based Metabonomics Study to Reveal the Progressive Metabolism Regulation of SAP Deficiency on ApoE-/- Mice.

Atherosclerosis is the most common disease of the vascular system and the metabolic disorder is one of its important molecular mechanisms. SAP protein is found to be highly expressed in atherosclerotic blood vessels. Our previous study found that SAP deficiency can significantly inhibit the development of atherosclerosis. However, the regulatory effect of SAP deficiency on AS metabolism is unknown. Based on 1H-NMR metabonomics, this study investigated the serum metabolic changes in ApoE-/-;SAP-/- mice compared with ApoE-/- mice during the whole progression of atherosclerosis. The results showed that acetate, pyruvate, choline and VLDL + LDL were statistically regulated to the normal levels as in C57 mice by SAP deficiency in ApoE-/-;SAP-/- mice at 8 w (without obvious plaques). With the appearance and aggravation of atherosclerotic plaques (8 + 4 w and 8 + 8 w), the four metabolites of acetate, pyruvate, choline and VLDL + LDL were continuously regulated, which were denoted as the metabolic regulatory markers of SAP deficiency. We also found that the changes in these four metabolites had nothing to do with high-fat diet. Therefore, it was revealed that SAP deficiency regulated the metabolic disorders in ApoE-/- prior to the appearance of obvious atherosclerotic plaques, which is one of the important mechanisms leading to the inhibition of atherosclerosis, providing a new basis for the application of SAP in atherosclerosis.

Ameliorative effect of Berberidis radix polysaccharide selenium nanoparticles against carbon tetrachloride induced oxidative stress and inflammation.

Berberidis radix polysaccharide (BRP) extracted as capping agents was applied to prepare BRP-selenium nanoparticles (BRP-SeNPs) in the redox reaction system of sodium selenite and ascorbic acid. The stability and characterization of BRP-SeNPs were investigated by physical analysis method. The results revealed that BRP were tightly wrapped on the surface of SeNPs by forming C-O⋯Se bonds or hydrogen bonding interaction (O-H⋯Se). BRP-SeNPs presented irregular, fragmented and smooth surface morphology and polycrystalline nanoring structure, and its particle size was 89.4 nm in the optimal preparation condition. The pharmacologic functions of BRP-SeNPs were explored in vitro and in vivo. The results showed that BRP-SeNPs could heighten the cell viabilities and the enzyme activity of GSH-Px and decrease the content of MDA on H2O2-induced AML-12 cells injury model. In vivo tests, the results displayed that BRP-SeNPs could increase the body weight of mice, promote the enzyme activity like SOD and GSH-Px, decrease the liver organ index and the hepatic function index such as ALT, AST, CYP2E1, reduce the content of MDA, and relieve the proinflammation factors of NO, IL-1ß and TNF-α in CCl4-induced mice injury model. Liver tissue histopathological studies corroborated the improvement of BRP-SeNPs on liver of CCl4-induced mice. The results of Western blot showed that BRP-SeNPs could attenuate oxidant stress by the Nrf2/Keap1/MKP1/JNK pathways, and downregulate the proinflammatory factors by TLR4/MAPK pathway. These findings suggested that BRP-SeNPs possess the hepatoprotection and have the potential to be a green liver-protecting and auxiliary liver inflammation drugs.

An integrated metabonomics study to reveal the inhibitory effect and metabolism regulation of taurine on breast cancer.

Breast cancer is a common metastatic malignant tumor in women. Taurine has been found to have anti-tumor effects on a variety of cancers. However, to the best of our knowledge, the role of taurine in the metastasis of breast cancer has not been reported. Thus, this study examined the effects of taurine on the growth and lung metastasis of breast cancer. Furthermore, the metabolism of serum, tumor tissue, and lung metastasis tissue were studied in a 4T1 subcutaneously transplanted breast cancer model through the integration of a 1H NMR-based metabonomics approach and histopathological assessments. The results showed that taurine significantly attenuated the tumor growth and lung metastasis, improved the pathological structure of tumor and lung tissue, and improved the metabolic disorders in 4T1 breast cancer mice. Additionally, taurine reversed the changes in serum lactate, creatine, and choline caused by the progression of breast cancer tumors. The levels of leucine/isoleucine, valine, alanine, arginine, methionine, glutamate, histidine, trimethylamine oxide (TMAO), taurine, and glucose in tumor tissues decreased, with an increment in lipids, lactate, and N-acetyl glycoprotein. Also, there was a reversal of leucine/isoleucine, valine, lactate, arginine, N-acetyl glycoprotein, glutamate, histidine, choline, and glycerophosphocholine/phosphocholine (GPC/PC) in the lung tissues. These metabolites changes were involved in the metabolic pathways of glycolysis, choline, amino acid, and lipid, suggesting that taurine exerted anti-breast cancer effects through the regulation of the underlying metabolism. This study provides a scientific basis for the adoption of taurine in the treatment of breast cancer metastasis.

A functional polysaccharide from Eriobotrya japonica relieves myocardial ischemia injury via anti-oxidative and anti-inflammatory effects.

We herein report a food-derived polysaccharide (EJP) with the effect of relieving myocardial ischemia reperfusion injury (MIRI). This novel polysaccharide was isolated from the leaf of Eriobotrya japonica, and we first found its myocardium protective effects in vitro. Then, we firstly characterized EJP with a series of analytical technologies and further tested its effect on myocardial ischemia reperfusion injury (MIRI) with the illustration of the potential mechanisms in vivo. Interestingly, in the murine model of MIRI, administration of EJP effectively improved post-I/R heart contraction and limited the infarct size. Moreover, EJP significantly attenuated IR-induced oxidative damage and inflammatory reaction, as evidenced by decreasing MDA, IL-6, and TNF-α contents and increasing SOD activity and GSH-Px expression. In addition, we proved that EJP not only had no nephrotoxicity but also demonstrated a protective effect on the kidneys through HE staining and biochemical analysis. In sum, EJP, with a significant protective effect against myocardial I/R injury by showing anti-inflammatory and anti-oxidative activities, may become a meaningful drug candidate for the treatment of myocardial I/R injury.

Systematic analysis of the lysine malonylome in Sanghuangporus sanghuang.

BACKGROUND: Sanghuangporus sanghuang is a well-known traditional medicinal mushroom associated with mulberry. Despite the properties of this mushroom being known for many years, the regulatory mechanisms of bioactive compound biosynthesis in this medicinal mushroom are still unclear. Lysine malonylation is a posttranslational modification that has many critical functions in various aspects of cell metabolism. However, at present we do not know its role in S. sanghuang. In this study, a global investigation of the lysine malonylome in S. sanghuang was therefore carried out. RESULTS: In total, 714 malonyl modification sites were matched to 255 different proteins. The analysis indicated that malonyl modifications were involved in a wide range of cellular functions and displayed a distinct subcellular localization. Bioinformatics analysis indicated that malonylated proteins were engaged in different metabolic pathways, including glyoxylate and dicarboxylate metabolism, glycolysis/gluconeogenesis, and the tricarboxylic acid (TCA) cycle. Notably, a total of 26 enzymes related to triterpene and polysaccharide biosynthesis were found to be malonylated, indicating an indispensable role of lysine malonylation in bioactive compound biosynthesis in S. sanghuang. CONCLUSIONS: These findings suggest that malonylation is associated with many metabolic pathways, particularly the metabolism of the bioactive compounds triterpene and polysaccharide. This paper represents the first comprehensive survey of malonylation in S. sanghuang and provides important data for further study on the physiological function of lysine malonylation in S. sanghuang and other medicinal mushrooms.

Post-screening characterization of an acidic polysaccharide from Echinacea purpurea with potent anti-inflammatory properties in vivo.

We extracted and purified three polysaccharides from Echinacea purpurea using pectinase-assisted extraction to obtain crude preparations and optimized the method using an orthogonal analysis. We obtained three polysaccharide fractions (EPPS-1, -2 and -3) using DEAE ion exchange and gel filtration chromatography. The homogeneity of the fractions was confirmed using high performance gel permeation chromatography. EPPS-3 administered to mice in a LPS-induced septicemia model effectively counteracted the effects of LPS resulting in significantly less lung damage. This trend was also seen in the serum and lung cytokine levels where EPPS-3 significantly decreased the levels of TNF-α and IL-6 and increased IL-10. Particularly, we fully characterized the structure of the EPPS-3 polysaccharide using a series of technologies. This polysaccharide structure was mainly composed of →4)-α-Glcp-(1→, →4)-α-Galp-(1→, T-α-Araf-(1→, →3,4)-ß-GalpA-(1→ glycosidic linkages at a certain proportion. In sum, EPPS-3, with a clear structure, has potent anti-inflammatory activities and is a candidate for further development as an anti-inflammatory agent for clinical development.

Polysaccharide from Echinacea purpurea reduce the oxidant stress in vitro and in vivo.

Echinacea purpurea polysaccharides (EPPS) were extracted through water extract and alcohol precipitate method. Three polysaccharides were purified by DEAE cellulose, named EPPS-1, EPPS-2 and EPPS-3. The antioxidant activities in three polysaccharides were screened by free radical scavenging test and EPPS-3 possessed the best antioxidant function. Then the antioxidant activities of EPPS-3 were further explored in oxidative damage model in vitro and in vivo for the first time. The results showed that the antioxidases and the metabolism content were significantly improved in EPPS-3 group. EPPS-3 could protect hepatic tissue from the injury of CCl4 compared with the oxidative damage model. The mechanism research demonstrated that EPPS-3 restrained cell apoptosis and promoted Nrf2 cell signal pathway to play an antioxidant impact. Therefore, EPPS-3 an ingredient could be served as amazing gift for food industry and feed additive.

Kaempferol-3-O-glucorhamnoside inhibits inflammatory responses via MAPK and NF-κB pathways in vitro and in vivo.

Klebsiella pneumoniae causes severe infections including pneumonia and sepsis and treatments are complicated by increased levels of antibiotic resistance. We have identified a flavonoid kaempferol-3-O-glucorhamnoside derived from the plant Thesium chinense Turcz that possessed potent anti-inflammatory effects in K. pneumoniae infected mice. Administration of kaempferol-3-O-glucorhamnoside before bacterial challenge effectively suppressed expression of the major inflammatory cytokines TNF-α, IL-6, IL-1ß and PGE2 and ameliorated lung edema. In addition, administration of this compound to cultured RAW macrophages or Balb/c mice resulted in the suppression of NFκB and MAP kinase phosphorylation indicating an inhibitory effect on inflammation in vitro and in vivo. Kaempferol-3-O-glucorhamnoside also decreased ROS levels and overall oxidative stress in lungs and in cultured cells generated by K. pneumoniae exposure. Taken together, kaempferol-3-O-glucorhamnoside is a potent anti-inflammatory in vitro and in vivo and is a promising therapeutic agent for treating K. pneumoniae infections in the clinic.

Quantification of in vivo gastric fluid volume in Bama miniature pigs in fasted state.

Although the study of bioequivalence waivers in humans is already well-established, their application and translation into animals, which are complicated by differences in physiology, have only recently become subjects of interest. The main purpose of this paper is to quantify the liquid volume affecting drug dissolution in pig stomachs. We used magnetic resonance imaging (MRI) to scan 18 Bama miniature pigs weighing 15, 30 or 50 kg. Amira 6.0.1 software was used for 3D image processing. We found that the gastric fluid volume had a linear relationship with the weight of pig (R2  = 0.9935) over this weight range. The pig weight, therefore, could be used as a surrogate for the fasted gastric fluid volume. After combining data of gastric fluid secretion and drinking water volumes, our results could be used as a reference for the evaluation of oral drug absorption in pigs.

The antioxidant action and mechanism of selenizing Schisandra chinensis polysaccharide in chicken embryo hepatocyte.

The antioxidant action and mechanism of selenizing schisandra chinensis polysaccharide (sSCP) were investigated in chicken embryo hepatocyte (CEH) taking schisandra chinensis polysaccharide (SCP) and N-acetyl-L-cysteine (NAC) as control. The CEH was cultured and treated with sSCP, then exposed to H2O2. The CEHs' viability, apoptosis, ROS and antioxidase contents and the protein expression in MAPKs pathway and mitochondrion-dependence apoptotic signal pathway were assayed. The results showed that sSCP could significantly raise the cell viability and the activities of SOD, CAT and GSH-Px, decrease the cell apoptosis and the content of LDH, AST, ALT and MDA, down-regulate the protein expression of p-JNK1, p-ERK1/2, p-p38, Bax, Caspase 3 and cytochrome C, and up-regulate the protein expression of Bcl-2 in comparison with H2O2 control group. The action of sSCP were stronger than those of SCP and NAC. These results indicated that selenylation modification could significantly enhance the antioxidant activity of SCP, sSCP could significantly protect hepatocyte from oxidative damage induced by H2O2, and its mechanism was by regulating the protein expression in MAPKs and mitochondrion-dependence apoptotic signaling pathways.

The antioxidative and hepatoprotective effects comparison of Chinese angelica polysaccharide(CAP)and selenizing CAP (sCAP) in CCl4 induced hepatic injury mice.

Chinese angelica polysaccharides (CAP) and selenizing CAP (sCAP) were prepared and identified through FTIR and SEM observation. Their antioxidant activities in vitro and hepatoprotective effects in vivo were compared by free radical-scavenging tests or with CCl4-induced hepatic injury model mice. The results showed that for DPPH radical, superoxide anion and hydroxyl radical, the scavenging capabilities of sCAP were significantly stronger than those of CAP. In hepatic injury model mice, sCAP could significantly reduce ALT, AST and ALP contents and raised TP content in serum, significantly reduce MDA and ROS contents and raised SOD and T-AOC activities in liver homogenate in comparison with CAP; obviously relieve the pathological changes of liver and significantly inhibit the expressions of p-ERK, p-JNK and p-p38 protein as compared with those in model control group. These results indicate that selenylation modification can enhance the antioxidant and hepatoprotective actions of Chinese angelica polysaccharide. A action mechanism of sCAP is suppressing the protein expression of MAPK signaling pathway.

Modification of lily polysaccharide by selenylation and the immune-enhancing activity.

Lily polysaccharide (LP) was extracted, purified and selenizingly modified by HNO3-Na2SeO3 method according to L9(3(4)) orthogonal design. Nine selenizing LPs, sLP1-sLP9, were obtained and their immune-enhancing activities were compared taking unmodified LP as control. The results in vitro test showed that sLP6 presented the strongest activity in promoting lymphocytes proliferation in single and synergetic with PHA, and the relative expression level of IL-2, IL-6 and IFN-γ mRNA of chicken peripheral lymphocytes. The results in vivo test showed that sLP6 could promote lymphocytes proliferation and enhance the serum antibody titers and serum IL-2, IL-6, IFN-γ contents more significantly than LP in chickens vaccinated with Newcastle Disease (ND) vaccine. These results indicate that polysaccharide selenizing can significantly enhance the immune-enhancing activity of LP and the optimal modification conditions are 400 mg of Na2SeO3 per 500 mg of LP, the reaction temperature of 70 °C and the reaction time of 6 h.

Optimization of selenylation modification for garlic polysaccharide based on immune-enhancing activity.

Garlic polysaccharide (GPS) was modified in selenylation respectively by nitric acid-sodium selenite (NA-SS), glacial acetic acid-selenous acid (GA-SA), glacial acetic acid-sodium selenite (GA-SS) and selenium oxychloride (SOC) methods each under nine modification conditions of L9(3(4)) orthogonal design and each to obtain nine selenizing GPSs (sGPSs). Their structures were identified, yields and selenium contents were determined, selenium yields were calculated, and the immune-enhancing activities of four sGPSs with higher selenium yields were compared taking unmodified GPS as control. The results showed that among four methods the selenylation efficiency of NA-SS method were the highest, the activity of sGPS5 was the strongest and significantly stronger than that of unmodified GPS. This indicates that selenylation modification can significantly enhance the immune-enhancing activity of GPS, NA-SS method is the best method and the optimal conditions are 0.8:1 weight ratio of sodium selenite to GPS, reaction temperature of 70 °C and reaction time of 10h.

The Selenylation Modification of Epimedium Polysaccharide and Isatis Root Polysaccharide and the Immune-enhancing Activity Comparison of Their Modifiers.

Epimedium polysaccharide (EPS) and isatis root polysaccharide (IRPS) were extracted, purified, and selenizingly modified by nitric acid-sodium selenite method to obtain nine selenizing EPSs (sEPSs), sEPS1-sEPS9 and nine selenizing IRPSs (sIRPSs), sIRPS1-sIRPS9, respectively. Their effects on chicken peripheral lymphocyte proliferation in vitro were compared by MTT assay. The results showed that selenium polysaccharides at appropriate concentration could promote lymphocyte proliferation more significantly than unmodified polysaccharides, sEPS5 and sIRPS5 with stronger actions were picked out and injected into the chickens vaccinated with Newcastle disease vaccine in vivo tests. The peripheral lymphocyte proliferation and serum antibody titer were determined. The results showed that sEPS5 and sIRPS5 could elevate serum antibody titer and promote lymphocyte proliferation more significantly than unmodified polysaccharides, sEPS5 possessed the strongest efficacy. These results indicate that selenylation modification can significantly enhance the immune-enhancing activity of EPS and IRPS, and sEPS5 can be as a new-type immunopotentiator of chickens.

Effects of Selenylation Modification on Antioxidative Activities of Schisandra chinensis Polysaccharide.

The selenylation modification of Schisandra chinensis polysaccharide (SCP) was conducted by the HNO3-Na2SeO3 method respectively under nine conditions according to L9(34) orthogonal design. Nine selenizing SCPs, sSCP1-sSCP9, were obtained, and their antioxidant activities were compared. In vitro test, the free radical-scavenging rates of nine sSCPs were determined for DPPH., .OH and ABTS+. sSCP1 presented the most significant effect, and could inhibit the nonenzymatic protein glycation. In vivo test, 14-day-old chickens were injected respectively with sSCP1 and SCP, the serum contents of CAT, SOD and MDA were determined. The result showed that as compared with the SCP group, the SOD and CAT activities were significantly or numerically raised and MDA content was significantly or numerically lowered in the sSCP1 group. These results indicate that selenylation modification can significantly enhance the antioxidant and antiglycative activity of SCP in vitro or in vivo. sSCP1 possesses the best efficacy and its modification conditions can be as optimal modification conditions that were 200 mg of Na2SeO3 for 500 mg of SCP, reaction temperature of 50°C and reaction time of 6 h.

Effects of selenizing angelica polysaccharide and selenizing garlic polysaccharide on immune function of murine peritoneal macrophage.

The effects of two selenizing polysaccharides (sCAP2 and sGPS6) on immune function of murine peritoneal macrophages taking two non-selenizing polysaccharides (CAP and GPS) and modifier Na2SeO3 as control. In vitro test, the changes of selenizing polysaccharides, non-selenizing polysaccharides and Na2SeO3 on murine macrophages function were evaluated by phagocytosis and nitric oxide (NO) secretion tests. In vivo test, the mice were injected respectively with 0.2, 0.4 and 0.6 mg of sCAP2, sGPS6, CAP and GPS, or Na2SeO3 80 µg or normal saline 0.4 mL. The peritoneal macrophages were collected and cultured to determine the contents of TNF-α, IL-6 and IL-10 in supernatants by enzyme-linked immunosorbent assay. The results showed that sCAP2 and sGPS6 could significantly promote the phagocytosis and secretion of NO and three cytokines of macrophages in comparison with CAP and GPS. sCAP2 possessed the strongest activity. This indicates that selenylation modification can further improve the immune-enhancing activity of polysaccharide, and sCAP2 could be as a new immunopotentiator.

Effect of selenylation modification on immune-enhancing activity of Atractylodes macrocephala polysaccharide.

The Atractylodes macrocephala polysaccharide (AMP) was extracted purified and modified in selenylation by Nitric acid-sodium selenite method to get nine selenizing AMPs (sAMPs), sAMP(1)-sAMP(9). In vitro test their effects on chicken peripheral lymphocyte proliferation were determined by MTT assay. The results showed that nine sAMPs and AMP at five concentrations could significantly promote lymphocyte proliferation, the actions in six sAMPs were significantly stronger than that in AMP, and in sAMP(9) was the strongest. In vivo test, 14-day-old chickens vaccinated with ND vaccine were injected respectively with sAMP(9) and AMP, the peripheral lymphocytes proliferation, serum antibody titer, IFN-γ, IL-2 and IL-6 contents were determined. The results displayed that the sAMP could significantly promote lymphocyte proliferation and elevate the antibody titers and content of IFN-γ, IL-2 and IL-6 in comparison with unmodified AMP. These results indicate that selenylation modification can significantly enhance the immune-enhancing activity of AMP.