Integral kinetic model for studying quercetin degradation and oxidation as affected by cholesterol during heating

The degradation and oxidation of quercetin, as affected by cholesterol during heating at 150 °C, was kinetically studied using non-linear regression models. Both TLC and HPLC were used to monitor the changes of quercetin, cholesterol and cholesterol oxidation products (COPs) during heating. The formation of COPs, including triol, 7-keto, 7α-OH and 7β-OH, was completely inhibited during the initial 30 minute heating period in the presence of 0.02% quercetin, accompanied by reduction in cholesterol peroxidation and degradation. However, the quercetin degradation or oxidation proceeded fast, with the rate constants (h(-1)) in the presence of nitrogen, oxygen and the combination of oxygen and cholesterol being 0.253, 0.868 and 7.17, respectively. When cholesterol and quercetin were heated together, the rate constants (h(-1)) of cholesterol peroxidation, epoxidation and degradation were 1.8 × 10(-4), 0.016 and 0.19, respectively. The correlation coefficients (r(2)) for all the oxidative and degradation reactions ranged from 0.82-0.99. The kinetic models developed in this study may be used to predict the degradation and oxidation of quercetin as affected by cholesterol during heating.     

Cholesterol oxidation in heated lard enriched with two levels of cholesterol

Cholesterol oxidation in lard containing two levels of added cholesterol was monitored using capillary gaschromatography. Loss of cholesterol and formation of cholesterol oxidation products (COPs) were measured. Lard samples with 10 times (Test I) and 2 times (Test II) the amount of cholesterol originally found in each batch of lard were heated at 180°C for 10 hr a day for 240 and 160 hr, respectively. Cholesterol steadily decreased throughout the heating period in both tests. Cholesterol loss followed a first-order reaction rate, with a rate constant (k) of −1.18×10⁻³ h⁻¹ for Test I and −9.45×10⁻³ h⁻¹ for Test II. The COPs accumulated during both heating tests. But the amount of COPs formed did not total the amount of cholesterol lost. During heating, thermal degradation of cholesterol likely occurred, and those products were not detected. During cooling, hydroperoxides formed, which further oxidized into the COPs that were detected. The 7-ketocholesterol and 5α,6α-epoxycholesterol were the predominant COPs formed. The isomeric 7α-and 7β-hydroxycholesterols also accumulated in the heating tests. The 3β,5α,6β-cholestantriol was found in very small amounts and the 25-hydroxycholesterol was not detected. Presented in part at the 80th AOCS Annual Meeting, Cincinnati, OH, in May, 1989.     

Cholesterol oxidation in some processed fish products

Numerous foods of animal origin are reported to contain considerable levels of cholesterol oxidation products (COP); however, very few reports are available on fish products. Levels of COP were assessed in samples of fish roe, fish oil, and fish meal. Among the fish roe samples, the smoked cod roe had the highest amount of COP, 93 μg/g lipids. Refined and bleached menhaden oil had 8 μg/g, and two experimental alkali-refined, bleached, and deodorized herring fish oil samples contained similar amounts of COP. The range of total COP in the three fish meal samples ranged from 50 to 78 μg/g fish meal. Generally, processed fish roe contained high amounts of COP compared with refined fish oils, which had very low amounts of COP. Fish meal samples had very high amounts of COP.     

Capabilities of different cooking oils in prevention of cholesterol oxidation during heating

The potential of various cooking oils to prevent cholesterol degradation and/or oxidation, as measured by the production of 7-ketocholesterol during heating at different temperatures, was studied using a cholesterol model system. In the control group (without cooking oil), cholesterol was relatively stable, and 73% of its initial concentration was present after 30 min of heating at 125°C. Less than 30 and 10% of cholesterol remained at 150 and 175°C after 30 min, respectively, and 10% at 200°C after 10 min. In the treatment group, cholesterol mixed with corn, canola, soybean, or olive oil had significantly improved thermal stability. More than 60 and 40% of cholesterol remained at 150 and 175°C after 30 min, respectively. In the control group, 7-ketocholesterol was produced when samples were heated above 150°C, and levels increased consistently during 30 min of heating. At 175 or 200°C, the level of 7-ketocholesterol did not increase further after reaching the highest level after 10 min of heating. 7-Ketocholesterol is not stable above 175°C, and its degradation rate could be much faster than its production at 200°C. 7-Ketocholesterol was not found in samples of cholesterol mixed with corn oil or laboratory-prepared soybean and rice bran oils until the heating temperature was raised to 175°C for 20 min. The levels of 7-ketocholesterol in those treatment groups were greater than that in the control group at 175°C for 30 min. These oils may increase the thermal stability of 7-ketocholesterol and retard its degradation rate.     

Health benefits of CLA – lessons from pig models in biomedical research

The objective of this review is to highlight the use of pig models for investigating safety, efficacy and the mechanisms of action of conjugated linoleic acid (CLA). Although CLA elicits positive effects in animal models and in vitro systems, a consistent concern in terms of translational research is that the health benefits observed by using these model systems cannot be extrapolated directly into humans. Conversely, the similarities between pigs and humans make the pig an ideal model for examining the health benefits of dietary supplements, functional foods and nutraceuticals. We have developed pig models of viral and bacterial infection to examine the preventive role of dietary CLA supplementation on virally induced immunosuppression and gut health, respectively. Results from these studies indicate that CLA significantly enhances the immune function while limiting the catabolic effects of uncontrolled immune and inflammatory responses. The scientific findings in pig models and human clinical trials demonstrate that CLA modulates immune responses in pigs and humans. Pig models of immunomodulation represent significant improvements over other animal models and in vitro systems because they mimic more closely the compartmentalization of the human immune system and the clinical presentation of human infectious, immune and inflammatory diseases.     

Cholesterol oxides content in selected animal products determined by GC‐MS

The aim of this study was to evaluate the effect of heat treatment of selected animal products on formation of cholesterol oxidation products (COP) and also to determine their content in selected pates and fermented pork sausage which are available on the Polish market. COP content in pates was significantly lower as compared to fermented sausages, and ranged from 39.5 to 43.1 µg/100 g; COP in sausages ranged from 195.8 to 263.4 µg/100 g of product. COP content in pan fried meats, chops, and fish fillets varied from 6.2 to 991.2 µg/100 g products. This paper demonstrates the method for determining the content of COP by the use of selected ion technique with the aid of MS. Practical applications: The method described is useful for the investigation of oxysterols in food matrices. The method is used for the investigation of the presence and content of COP, such as: 7β‐hydroxycholesterol, 5α,6α‐epoxycholesterol, 5β,6β‐epoxycholesterol, 5α‐cholestane‐3β,5β,6β‐triol, 7‐ketocholesterol, and 25‐hydroxycholesterol. The obtained data about COP content in selected animal products and their formation during heat treatment are crucial for creating a reliable database to assess their daily intakes and biological effects in humans.     

CLA formation in oils during hydrogenation process as affected by catalyst types,catalyst contents,hydrogen pressure,and oil species

The effects of types and amount of catalysts, hydrogen pressure, and kinds of vegetable oils on the formation of CLA isomers were studied during hydrogenation. CLA isomers were identified by using a silver ion-impregnated high-performance liquid chromatograph and 100-m cyano-capillary column gas chromatograph. A selective catalyst (SP-7) produced a considerably higher content of CLA in soybean oil than nonselective catalysts. The maximal quantity of CLA produced in soybean oil during hydrogenation increased greatly with increasing amount of catalyst. By increasing the amount of selective catalyst from 0.05 to 0.3%, the quantity of total CLA obtained was about 1.9 times higher. Changes in hydrogen pressure also greatly influenced total CLA formed. By decreasing hydrogen pressure from 0.24 to 0.024 MPa, the quantity of CLA obtained was about 1.3 times higher. With different oil species (soybean, cottonseed, and corn oils), the time to reach the maximal quantity of CLA was different under the same hydrogenation conditions. However, the maximal quantity of CLA and proportion of CLA isomers formed were almost identical, regardless of oil species tested, under the same hydrogenation conditions.     

Effect of α‐, γ‐, and δ‐tocopherol on the distribution of volatile secondary oxidation products in fish oil

The relative ability of α‐, γ‐ and δ‐tocopherol (TOH) to influence the distribution of volatile secondary oxidation products in fish oil was studied, with particular emphasis on oxidation products expected to be important for adverse flavour formation. Purified fish oil samples with 100 ppm or 1000 ppm of the different tocopherols were analysed by dynamic headspace analysis of the volatiles formed after 2, 5 and 8 d of storage at 30 �C. The tocopherol type and concentration affected not only the overall formation of volatile secondary oxidation products, but also the composition of this group of oxidation products. Principal component analysis of the data obtained suggested that high tocopherol hydrogen‐donating power, i.e. a high tocopherol concentration or the use of αTOH as opposed to γTOH or δTOH, directs the formation of hydrocarbons, unsaturated carbonyl compounds of relatively high molecular weight, as well as the formation of cis, trans isomers of unsaturated aldehydes. Although an active inhibitor of overall volatile formation, αTOH at a high concentration thus appears to direct the formation of the more flavour‐potent aldehydes, such as those linking the carbonyl group with ethylenic conjugated unsaturation.     

Stability of bimetallic Bi–Pd and Pb–Pd carbon-supported catalysts during their use in glyoxal oxidation

The incorporation of Bi or Pb as promoting elements in Pd-based carbon-supported catalysts drastically increases the catalytic activity in the selective oxidation of glyoxal into glyoxylic acid. Because partial dissolution of the promoter was clearly demonstrated by atomic absorption analysis of the reaction medium, experiments are performed to examine the stability of these catalysts. Dissolution tests in the presence of the individual constituents of the reaction medium (glyoxal, glyoxylate, glycolate, oxalate) were carried out in air or nitrogen to identify the factors responsible for Pb or Bi leaching. Pb- or Bi-promoted Pd/C catalysts were prepared by thermal degradation of acetate-type precursors and characterized by X-ray diffraction and X-ray photoelectron spectroscopy before and after their use in glyoxal oxidation. Promoter leaching increases with the reaction time. Monometallic Bi/C and Pb/C catalysts were found to lose smaller amounts of promoting agent than the bimetallic M–Pd/C (M=Bi, Pb) catalysts. Losses are more pronounced from Pb–Pd/C catalysts than from their Bi-based partners. Both glyoxal and glyoxylate seem to be among the main factors responsible for the promoter losses in relation to their complexing properties.     

Studies on the oxidation of phenols catalyzed by a copper(II)–Schiff base complex in aqueous solution under mild conditions

The catalytic oxidation of phenol with hydrogen peroxide using a synthetic copper(II)–Schiff base complex as catalyst has been investigated in phosphate buffer at pH 7 and 25 °C. In order to further investigate the reaction pathway, the catalytic oxidation of hydroquinone, p‐benzoquinone and catechol were also studied under the same conditions. These reactions were found to be pseudo‐first‐order with respect to the concentration of phenolic substances. The rate constants were also calculated. In the presence of catalyst, the kinetics and the HPLC analysis showed that for the first step phenol was oxidized to hydroquinone and catechol, and the catalyst easily promoted the formation of hydroquinone but not catechol, for the second step the dihydroxybenzenes were further oxidized to benzoquinone, and lastly short‐chain acids, including maleic acid and oxalic acid, were formed. The activity of the catalyst hardly decreased during the whole reaction. Addition of imidazole accelerated the oxidation of phenol. The catalytic decomposition of hydrogen peroxide using this catalyst was also investigated. Copyright © 2005 Society of Chemical Industry     

Mercury removal from coal combustion by Fenton reactions – Part A: Bench-scale tests

This series of papers describes the development of technology to convert Hg(0) to Hg(II) in coal-derived flue gas based on the well-known Fenton reactions so that a Hg control strategy can be implemented in a wet scrubber. This effort consists of both bench-scale and pilot-scale work. This first paper reports on the bench-scale tests. The bench-scale results showed that Hg(0) oxidation can be achieved by the Fenton reactions and the oxidation rate is quantitatively dependent on the residence time of the Hg stream in the solution. An average of 75% oxidation of Hg(0) was achieved. Iron-based Fenton-type additives gave much more promising results compared to Cu-based Fenton-like additives for Hg(0) oxidation. The pH value of the sorbent solution also had a significant effect on the oxidation of Hg(0) and a suitable pH window was found to lie between 1.0 and 3.0 for this application. This may be attributed to the chain reaction mechanisms of Fe³⁺/H₂O₂ for Fenton reactions, i.e., the decomposition of H₂O₂ for the production of OOH radicals in the Fe³⁺/H₂O₂ system which is kinetically favoured under a wide range of conditions at pH values of 3 or less. At higher pH values, H₂O₂ is converted to H₂O instead of OOH radicals in the presence of Fe³⁺.     

Sol–gel derived CeO2/α‐Al2O3 bilayer thin film as an anti‐coking barrier and its catalytic coke oxidation performance

A CeO₂/α‐Al₂O₃ bilayer was coated on a high temperature alloy (Incoloy 800H) by sol–gel dip‐coating and was evaluated for its potential as an anticoking barrier and coke oxidation catalyst. The bilayer effectively functioned as a barrier to metal surface catalyzed coking. The film prevented filamentous catalytic coking via blocking surface active metallic sites on the Incoloy substrate. Furthermore, the bilayer reduced the oxidation temperature of pyrolytic coke deposited on the film surface as compared to a bare oxidized Incoloy substrate, mostly owing to the oxidation catalytic activity of the CeO₂ layer. Finally, it is demonstrated that the presence of the α‐Al₂O₃ buffer layer is critically important to the overall performance. Without the α‐Al₂O₃ layer, a CeO₂ layer nearly completely lost both its barrier and oxidation catalytic functions. It is presumed that metallic species migrating from the substrate during high temperature treatments are responsible for the CeO₂ deactivation, likely by blocking catalytic sites on the CeO₂ surface. © 2018 American Institute of Chemical Engineers AIChE J, 64: 4019–4026, 2018     

High thermal conductive β-SiC for selective oxidation of H2S: A new support for exothermal reactions

This study aims at synthesizing a new by substituting 1 atom% Pd²⁺ in ionic state in TiO₂ in the form of Ti_0.99Pd_0.01O_1.99 with oxide-ion vacancy. The catalyst was synthesized by solution combustion method and was characterized by XRD and XPS. The catalytic activity was investigated by performing CO oxidation, hydrocarbon oxidation and NO reduction. A reaction mechanism for CO oxidation by O₂ and NO reduction by CO was proposed. The model based on CO adsorption on Pd²⁺ and dissociative chemisorption of O₂ in the oxide-ion vacancy for CO oxidation reaction fitted the experimental for CO oxidation. For NO reduction in presence of CO, the model based on competitive adsorption of NO and CO on Pd²⁺, NO chemisorption and dissociation on oxide-ion vacancy fitted the experimental data. The rate parameters obtained from the model indicated that the reactions were much faster over this catalyst compared to other catalysts reported in the literature. The selectivity of N₂, defined as the ratio of the formation of N₂ and formation of N₂ and N₂O, was very high compared to other catalysts and 100% selectivity was reached at temperature of 350 °C and above. As the N₂O + CO reaction is an intermediate reaction for NO + CO reaction, it was also studied as an isolated reaction and the rate of the isolated reaction was less than that of intermediate reaction.     

Polymerization of acrylonitrile initiated by cerium (IV)‐oxalic acid redox system: A kinetic study

The kinetics of aqueous polymerization of Acrylonitrile initiated by the Cerium (IV)‐Oxalic acid redox system in Sulfuric acid medium has studied under nitrogen atmosphere in the temperature range of 25–50°C. The rate of polymerization (R_p) and the disappearance of Cerium (IV) have been measured. The water‐miscible organic solvents and inorganic salts were depressed both the rate and the conversion. The effects of ionic strength, effects of surfactant have been investigated. The temperature dependence of the rate was studied and the activation parameters were computed using Arrhenius and Eyring plots. A mechanism consistent with the experimental data, involving Ce(IV)–Oxalic acid complexation that generates free radical was suggested. The chain termination step of the polymerization reaction was determined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Directed Biosynthesis of Phytotoxic Alkaloids in the Cyanobacterium Nostoc 78–12A

Out of the green! Precursor‐directed biosynthesis allowed for the production of new nostocarboline derivatives that display phytotoxic and algicidal properties—in a phototrophic organism. The mechanism of action includes downregulation of photosynthesis, as demonstrated by chlorophyll‐a fluorescence imaging.

     

Simultaneous removal of COD and NH3‐N in secondary effluent of high‐salinity industrial waste‐water by electrochemical oxidation

BACKGROUND: Electrochemical oxidation has been applied successfully in industrial waste‐water treatment. The simultaneous removal of COD_Cr and NH₃‐N, as well as the corresponding mechanisms and reaction zone, were examined in this study. The reaction kinetics and the significant factors that affect removal performance were also studied. RESULTS: The COD_Cr removal efficiency without chlorides in waste‐water was only 11.8% after 120 min of treatment, which was much lower than the efficiency with chlorides, and agitation did not improve the performance. When the current density was increased from 2.5 to 10 mA cm^?2, the removal efficiency was improved. The removal efficiencies of COD_Cr and NH₃‐N were less at initial pH = 11 than at pH = 3 and 8.7 (without adjustment). The COD_Cr and NH₃‐N removal efficiencies were decreased by about 30% and 50%, respectively, when the electrode distance was increased from 4 to 12 cm. Instantaneous current efficiency decreased with increase in current density. CONCLUSIONS: The degradation of pollutants occurred mainly at the boundary layer between the electrode and the bulk solution. The indirect oxidation by active chlorine generated from the chlorides was proven to be the primary mechanism of electrochemical oxidation treatment. The removal of COD_Cr in this study followed a pseudo‐first‐order kinetic model. Copyright © 2011 Society of Chemical Industry     

Investigation of a 6‐MSA Synthase Gene Cluster in Aspergillus aculeatus Reveals 6‐MSA‐derived Aculinic Acid,Aculins A–B and Epi‐Aculin A

Aspergillus aculeatus, a filamentous fungus belonging to the Aspergillus clade Nigri, is an industrial workhorse in enzyme production. Recently we reported a number of secondary metabolites from this fungus; however, its genetic potential for the production of secondary metabolites is vast. In this study we identified a 6‐methylsalicylic acid (6‐MSA) synthase from A. aculeatus, and verified its functionality by episomal expression in A. aculeatus and heterologous expression in A. nidulans. Feeding studies with fully ¹³C‐labeled 6‐MSA revealed that 6‐MSA is incorporated into aculinic acid, which further incorporates into three compounds that we name aculins A and B, and epi‐aculin A, described here for the first time. Based on NMR data and bioinformatic studies we propose the structures of the compounds as well as a biosynthetic pathway leading to formation of aculins from 6‐MSA.