Use of Crude Glycerol as Sole Carbon Source for Microbial Lipid Production by Oleaginous Yeasts

Polyphenols of plant origin with wide range of antiradical activity can prevent diseases caused by oxidative and inflammatory processes. In this study, we show using ESR method that the purified water-soluble extract from leaves of Rhus typhina L. containing hydrolysable tannins and its main component, 3,6-bis-O-di-O-galloyl-1,2,4-tri-O-galloyl-β-d-glucose (C₅₅H₄₀O₃₄), displayed a strong antiradical activity against the synthetic 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) in homogenous (solution) and heterogeneous systems (suspension of DPPH containing liposomes) in the range of 1–10 μg/ml. The C₅₅H₄₀O₃₄ and extract at 1–30 μg/ml also efficiently, but to a various degree, decreased reactive oxygen and nitrogen species (RONS) formation induced in erythrocytes by oxidants, following the sequence: tert-butyl hydroperoxide (tBuOOH) > peroxynitrite (ONOO^?) >hypochlorous acid (HClO). The explanation of these differences should be seen in the specificity of scavenging different RONS types. These relationships can be represented for C₅₅H₄₀O₃₄ and the extract by the following order of selectivity: O^.? ₂ ≥ NO· > ·OH > ¹O₂. The extract exerted a more pronounced antiradical effect in reaction with DPPH and ROS in all models of oxidative stress in erythrocytes in comparison with C₅₅H₄₀O₃₄. The redox processes between the extract components and their specificity in relation to RONS can underlie this effect.     

Gamma Radiation-Induced Graft Copolymerization of Styrene Onto Polyethyleneterephthalate Films: Application in Fuel Cell Technology as a Proton Exchange Membrane

Polyethyleneterephthalate (PET) based proton exchange membrane for using in fuel cells was successfully prepared by gamma radiation-induced graft copolymerization of styrene monomer onto PET film and the consequent selective sulfonation of the grafting chain in the film state using chlorosulfonic acid (ClSO₃H). The effects of grafting conditions (e.g., monomer concentration, irradiation dose) on the degree of grafting and sulfonation condition (e.g., optimum concentration of ClSO₃H) on the degree of sulfonation were studied. The degree of grafting, the degree of sulfonation and the physico-chemical properties (such as, water uptake, mechanical strength, thermal durability, hydrolytic stability, oxidative stability) of the gamma radiation-induced grafted membrane were found to be better when compared to those of the UV-radiation grafted membrane. The membrane shows higher ion exchange capacity (0.9 mmol g^?1) and higher proton conductivity (0.075 S cm^?1), similar to those of Nafion membrane.     

Selective Hydrovinylation of Styrene in a Membrane Reactor: Use of Carbosilane Dendrimers with Hemilabile P,O Ligands

A codimerization of styrene and ethene can be carried out continuously in a nanofiltration membrane reactor with dendritic Pd complexes such as 1 . The selectivity of the reaction is increased considerably under continuous conditions. The activity and selectivity of monomeric model complexes and the dendritic catalysts were compared in batch reactions.     

Lactucin,a Bitter Sesquiterpene from Cichorium intybus,Inhibits Cancer Cell Proliferation by Downregulating the MAPK and Central Carbon Metabolism Pathway

Lung cancer, especially adenocarcinoma, is the second most occurring and highest fatality-causing cancer worldwide. Many natural anticancer compounds, such as sesquiterpene lactones (SLs), show promising anticancer properties. Herein, we examined Lactucin, an SL from the plant Cichorium intybus, for its cytotoxicity, apoptotic-inducing, cell cycle inhibiting capacity, and associated protein expression. We also constructed a biotinylated Lactucin probe to isolate interacting proteins and identified them. We found that Lactucin stops the proliferation of A549 and H2347 lung adenocarcinoma cell lines while not affecting normal lung cell MRC5. It also significantly inhibits the cell cycle at G₀/G₁ stage and induces apoptosis. The western blot analysis shows that Lactucin downregulates the MAPK pathway, cyclin, and cyclin-dependent kinases, inhibiting DNA repair while upregulating p53, p21, Bax, PTEN, and downregulation of Bcl-2. An increased p53 in response to DNA damage upregulates p21, Bax, and PTEN. In an activity-based protein profiling (ABPP) analysis of A549 cell’s protein lysate using a biotinylated Lactucin probe, we found that Lactucin binds PGM, PKM, and LDHA PDH, four critical enzymes in central carbon metabolism in cancer cells, limiting cancer cells in its growth; thus, Lactucin inhibits cancer cell proliferation by downregulating the MAPK and the Central Carbon Metabolism pathway.     

Quantitative Analysis of Previously Identified Propionate-Oxidizing Bacteria and Methanogens at Different Temperatures in an UASB Reactor Containing Propionate as a Sole Carbon Source

Propionate degradation is crucial for maintaining the efficiency and stability of an anaerobic reactor. However, there was little information about the effects of ecological factor on propionate-oxidizing bacteria (POB). In current research, quantitative real-time fluorescence polymerase chain reaction (QPCR) of some identified POB and methanogens with a decrease in temperature in an upflow anaerobic sludge bed (UASB) reactor containing propionate as sole carbon source was investigated. The results showed that there were at least four identified POB, including Pelotomaculum schinkii, Pelotomaculum propionicum, Syntrophobacter fumaroxidans, and Syntrophobacter sulfatireducens, observed in this UASB reactor. Among them, P. schinkii was dominated during the whole operational period. Its quantity was 1.2?×?10⁴ 16S rRNA gene copies per nanogram of DNA at 35 °C. A decrease in temperature from 35 to 30 °C led to P. schinkii to be increased by 1.8 times and then it was gradually reduced with a decrease in temperature from 30 to 25, 20, and 18 °C stepwise. A decrease in temperature from 35 to 20 °C did not make the amount of methanogens markedly changed, but hydrogenotrophic methanogens (Methanospirillum) and acetotrophic methanogens (Methanosaeta) at 18 °C were increased by an order of magnitude and 1.0 time, respectively, compared with other experimental conditions.     

Biodegradation of Bisphenol A and Decolorization of Synthetic Dyes by Laccase from White-Rot Fungus, Trametes polyzona

Purified laccase from Trametes polyzona WR710-1 was used as biocatalyst for bisphenol A biodegradation and decolorization of synthetic dyes. Degradation of bisphenol A by laccase with or without redox mediator, 1-hydroxybenzotriazole (HBT) was studied. The quantitative analysis by HPLC showed that bisphenol A rapidly oxidized by laccase with HBT. Bisphenol A was completely removed within 3 h and 4-isopropenylphenol was found as the oxidative degradation product from bisphenol A when identified by GC-MS. All synthetic dyes used in this experiment, Bromophenol Blue, Remazol Brilliant Blue R, Methyl Orange, Relative Black 5, Congo Red, and Acridine Orange were decolorized by Trametes laccase and the percentage of decolorization increased when 2 mM HBT was added in the reaction mixture. This is the first report showing that laccase from T. polyzona is an affective enzyme having high potential for environmental detoxification, bisphenol A degradation and synthetic dye decolorization.     

Guignardic Acid,a Novel Type of Secondary Metabolite Produced by the Endophytic Fungus Guignardia sp.: Isolation,Structure Elucidation,and Asymmetric Synthesis

A UV‐guided fractionation of the AcOEt extract of the fermentation broth of Guignardia sp., an endophytic fungus from the leaves of the tropical tree Spondias mombin, resulted in the identification of the new metabolite (−)‐(2S,5Z)‐2‐(1‐methylethyl)‐4‐oxo‐5‐(phenylmethylene)‐1,3‐dioxolane‐2‐carboxylic acid ( 1 ), isolated as NH salt 1a . The metabolite 1 was designated (−)‐(S)‐guignardic acid. This first member of a new class of natural compounds contains a dioxolanone moiety formed by fusion of 2‐oxo‐3‐phenylpropanoic acid (phenylpyruvic acid) and 3‐methyl‐2‐oxobutanoic acid (dimethylpyruvic acid), products of the oxidative deamination of phenylalanine and valine, respectively. The structure of 1a was deduced from spectral data (UV, IR, MS, ¹H‐ and ¹³C‐NMR) and confirmed by asymmetric synthesis.     

Kinetic Modeling as a Tool to Understand and Improve the Nitroxide Mediated Polymerization of Styrene

Kinetic modeling is used to obtain insight in the complex interplay between reaction rates and obtained polymer properties in the SG1 and the TEMPO mediated bulk polymerization of styrene at 396 K. The increase of the viscosity during NMP is accounted for. At higher targeted chain lengths, chain transfer to dimer and transfer from nitroxide to dimer are shown to cause the experimentally observed reduced control over the average polymer properties and to result in a clear fronting of the polymer chain length distribution. The potential of kinetic modeling to design tailor‐made synthesis strategies is illustrated. Simulations indicate that careful control of the polymerization conditions allows to obtain an important improvement of the polymer properties. The approach is also applicable for NMP mediated by other alkoxyamines/nitroxides and allows to expand the application range of NMP for styrene polymerization in particular to synthesize complex polymer architectures by assembly of functionalized polymers.

     

Multi-Physics Modeling of Solid Oxide Fuel Cell Fueled by Methane and Analysis of Carbon Deposition

Internal reformation of low steam methane fuel is important for the high e ciency and low cost operation of solid oxide fuel cell. Understanding and overcoming carbon deposition is crucial for the technology development. Here a multi-physics model is established for the relevant experimental cells. Balance of electrochemical potentials for the electrochemical reactions, generic rate expression for the methane steam reforming, dusty gas model in a form of Fick's model for anode gas transport are used in the model. Excellent agreement between the theoretical and experimental current-voltage relations is obtained, demonstrating the validity of the proposed theoretical model. The steam reaction order in low steam methane reforming reaction is found to be 1. Detailed information about the distributions of physical quantities is obtained by the numerical simulation. Carbon deposition is analyzed in detail and the mechanism for the coking inhibition by operating current is illustrated clearly. Two expressions of carbon activity are analyzed and found to be correct qualitatively, but not quantitatively. The role of anode diffusion layer on reducing the current threshold for carbon removal is also explained. It is noted that the current threshold reduction may be explained quantitatively with the carbon activity models that are only qualitatively correct.     

Composition and Microstructure Determination of the Syndiotactic Copolymer of para-Methylstyrene and Styrene by Pyrolysis Gas Chromatography

The composition and microstructure of syndiotactic para-methylstyrene/styrene copolymer was determined by a pyrolysis gas chromatography (Py-GC) method. This method uses the styrene and para-methylstyrene monomer peak intensities to determine the styrene and para-methylstyrene composition in the copolymer. The number average sequence length of styrene was calculated by using the triad peak intensities. Because of the low concentration of para-methylstyrene in the copolymer, the number average sequence length of para-methylstyrene was determined with formulas that incorporate the copolymer composition and the number average sequence length of styrene. The distribution of para-methylstyrene defined by the terms “percent of single units” and “percent of desired distribution” was calculated by the number average sequence of para-methylstyrene. This method has been tested with copolymers containing up to 24 mole% of para-methylstyrene. The composition results from Py-GC of para-methylstyrene and styrene copolymers used in this study were in excellent agreement with ¹H-NMR results.     

Molecular Modeling in Chromatoscopy as a New Tool in the Structure Elucidation of Novel Isomers by GC/MS

The importance of gas–solid chromatography on graphitized thermal carbon black (GTCB) as a source of additional data for the positive structural elucidation of novel isomers by gas chromatography–mass spectrometry is discussed. The retention parameters of isomers being investigated were calculated by Kiselev's method (chromatoscopy) to predict the order of their separation on a column packed with GTCB. To extend the possibilities of this method and to improve the accuracy of a prediction of retention parameters, the molecular mechanics was used for the optimization of hypothetical molecular models of isomers required for these calculations. As a test mixture 11 isomers of perhydroanthracene and perhydrophenanthrene were consedered. The predicted elution order from the column packed with GTCB of these isomers, calculated on the basis of molecular models optimized by molecular mechanics appeared to be close to the experiment, whereas the result obtained by a conventional approach appeared to fail. Molecular modeling in chromatoscopy was used for the structural elucidation of novel isomers of perhydroxanthene (PHX) and perhydro-4-thia-s-indacene (PHTI), which were found by GC–MS in reaction mixtures. The evidence for this assignment-based on the obtained GC and MS data, is discussed.     

Solubility Optimization of Loxoprofen as a Nonsteroidal Anti-Inflammatory Drug: Statistical Modeling and Optimization

Industrial-based application of supercritical CO₂ (SCCO₂) has emerged as a promising technology in numerous scientific fields due to offering brilliant advantages, such as simplicity of application, eco-friendliness, and high performance. Loxoprofen sodium (chemical formula C₁₅H₁₈O₃) is known as an efficient nonsteroidal anti-inflammatory drug (NSAID), which has been long propounded as an effective alleviator for various painful disorders like musculoskeletal conditions. Although experimental research plays an important role in obtaining drug solubility in SCCO₂, the emergence of operational disadvantages such as high cost and long-time process duration has motivated the researchers to develop mathematical models based on artificial intelligence (AI) to predict this important parameter. Three distinct models have been used on the data in this work, all of which were based on decision trees: K-nearest neighbors (KNN), NU support vector machine (NU-SVR), and Gaussian process regression (GPR). The data set has two input characteristics, P (pressure) and T (temperature), and a single output, Y = solubility. After implementing and fine-tuning to the hyperparameters of these ensemble models, their performance has been evaluated using a variety of measures. The R-squared scores of all three models are greater than 0.9, however, the RMSE error rates are 1.879 × 10⁻⁴, 7.814 × 10⁻⁵, and 1.664 × 10⁻⁴ for the KNN, NU-SVR, and GPR models, respectively. MAE metrics of 1.116 × 10⁻⁴, 6.197 × 10⁻⁵, and 8.777 × 10⁻⁵errors were also discovered for the KNN, NU-SVR, and GPR models, respectively. A study was also carried out to determine the best quantity of solubility, which can be referred to as the (x₁ = 40.0, x₂ = 338.0, Y = 1.27 × 10⁻³) vector.     

Enhanced Sensitivity of 4‐Chlorophenol Detection by Use of Nitrobenzene as a Liquid Membrane over a Carbon Nanotube‐Modified Glassy Carbon Electrode

The analytical utility of nitrobenzene as a liquid membrane for the detection of hydrophobic compounds was examined with a glassy carbon electrode, using 4‐chlorophenol as the model analyte. Electrochemical experiments indicated a large partition coefficient for the entry of 4‐chlorophenol into the nitrobenzene (7.6×10²±1.5×10²). This was combined with an increase in effective electrode area by coating with single‐walled nanotubes. Differential pulse voltammetry produced a linear response across the range 0.3 nM to 1.5 nM with a sensitivity of 1.1×10^?5 A nM^?1 cm^?2. To the best of our knowledge, this limit of detection for phenol is lower than other nonenzymatic modifications of carbon.     

A Study of the Composition of Water Vapor Saturated Natural Gas,as Applied to Elucidation of the Nature of Vapor-Gas Thermal Phenomena

The composition of water vapor saturated gases of various temperatures from reserve wells of Yangantau health resort was studied. The dependence of the concentration and composition of organic substances from the vapor condensate and of the extent of thermal oxidative degradation of the shale organic matter on the rock temperature in the heating zone was examined.     

Modeling the Biomass Growth and Enzyme Secretion by the White Rot Fungus Phanerochaete chrysosporium: a Stochastic-Based Approach

The white rot fungus Phanerochaete chrysosporium has been identified to be an environmentally useful microorganism for the degradation of various hazardous pollutants, mainly because of its ligninolytic enzyme system, particularly the lignin peroxidase (LiP) secreted by the fungus. In the present work, the behavior of the fungus in liquid medium due to variation in physico-chemical parameters, i.e., glucose concentration, nitrogen concentration, agitation, etc., was studied. Increment of the initial concentration of glucose in the medium increases the biomass growth and LiP activity, when cultured under controlled conditions. The biomass growth and LiP activity by the fungus was modeled following stochastic approach. The behavior of growth and enzyme activity of the fungus observed from the model were found to be in agreement with the experiments qualitatively.     

Structure Elucidation and Theoretical Investigation of Key Steps in the Biogenetic Pathway of Schisanartane Nortriterpenoids by Using DFT Methods

Rubrifloradilactone C ( 4 ), a novel bioactive nortriterpenoid, along with four other nortriterpenoids ( 1 – 3 , 5 ) were isolated from Schisandra rubriflora. The structure of 4 was determined by extensive NMR spectral analysis, computational evidence by using the GIAO method at the B3LYP/6–311++G(2d,p)//B3LYP/6–31G(d) levels, and X‐ray analysis. DFT at the B3LYP/6–311+G(d,p) level was selected to clarify the key mechanistic steps in the formation of 1 and 4 through transition‐state (TS) investigations. The effect of enzymes on the TS barriers was considered by using the polarized continuum model. Other possible products based on the new mechanism were predicted.