Prediction of Klason lignin and lignin thermal degradation products by Py-GC/MS in a collection of Lolium and Festuca grasses

A rapid method for the analysis of biomass feedstocks was established to identify the quality of the pyrolysis products likely to impact on bio-oil production. A total of 15 Lolium and Festuca grasses known to exhibit a range of Klason lignin contents were analysed by pyroprobe-GC/MS (Py-GC/MS) to determine the composition of the thermal degradation products of lignin. The identification of key marker compounds which are the derivatives of the three major lignin subunits (G, H, and S) allowed pyroprobe-GC/MS to be statistically correlated to the Klason lignin content of the biomass using the partial least-square method to produce a calibration model. Data from this multivariate modelling procedure was then applied to identify likely "key marker" ions representative of the lignin subunits from the mass spectral data. The combined total abundance of the identified key markers for the lignin subunits exhibited a linear relationship with the Klason lignin content. In addition the effect of alkali metal concentration on optimum pyrolysis characteristics was also examined. Washing of the grass samples removed approximately 70% of the metals and changed the characteristics of the thermal degradation process and products. Overall the data indicate that both the organic and inorganic specification of the biofuel impacts on the pyrolysis process and that pyroprobe-GC/MS is a suitable analytical technique to asses lignin composition. © 2007 Elsevier B.V. All rights reserved.

Cytotoxicity of monomers, plasticizer and degradation by-products released from dental hard chairside reline resins

Objectives. The aim of this study was to evaluate the cytotoxic effect of the monomers isobutyl methacrylate (IBMA) and 1,6-hexanediol dimethacrylate (1,6-HDMA), the plasticizer di-n-butyl phthalate (DBP), and the degradation by-products methacrylic acid (MA) and benzoic acid (BA) on L929 cells. Based on previous investigations on the release of these compounds from hard chairside reline resins, a range of concentrations (mu mol/L) were selected for the cytotoxicity tests (IBMA, 5.491406.57; 1,6-HDMA, 1.2239.32; DBP, 1.12143.8; MA, 9.07581; BA, 3.19409).Methods. Cytotoxic effects were assessed using MTT and 3H-thymidine assays after the cells had been exposed to the test compounds at the given concentrations for 24h. Cytotoxicity was rated based on cell viability relative to controls (cells exposed to medium without test substances).Results. DNA synthesis activity was inhibited by all compounds. Mitochondrial dehydrogenase activity decreased in cells treated with monomers, plasticizer and MA by-product, whereas no cytotoxic effect was observed on contact with BA at the majority of concentrations tested. The ranges of suppression for 3H-thymidine assay were: IBMA, 2595%; 1,6-HDMA, 9598%; DBP, 4098%; MA, 9799%; BA, 5471%. For MTT assay, the ranges of suppression were: IBMA, 096%; 1,6-HDMA, 2689%; DBP, 1780%; MA, 5266%; BA, 027%. The 3H-thymidine assay was more sensitive than the MTT assay.Significance. This study evaluated the cytotoxicity of a wide range of concentrations of monomers (IBMA and 1,6-HDMA), plasticizer (DBP) and degradation by-products (MA and BA), including those expected to be released from hard chairside reline resins. The differences observed in the cytotoxicity of these compounds, along with other properties, may assist the dental practitioners in the selection of reline materials with improved service life performance and low risk of adverse reactions in patients who wear relined dentures.

CHEMICAL DEGRADATION OF ESFENVALERATE AND HPLC-UV-PAD DETECTION OF INTERMEDIATES AND BY-PRODUCTS

The impact of pyretroids, their by-products and degradation products on humans and the environment is recognized as a serious problem. Despite several studies regarding esfenvalerate toxicity and its detection in water and sediments, there is still a lack of information about its degradation intermediates and by-products in water. In this work, an HPLC method was developed to follow up the degradation of esfenvalerate and to detect the intermediates and by-products formed during the chemical degradation process. The chemical degradation was performed using an esfenvalerate suspension and different concentrations of hydrogen peroxide, temperatures, and pH. The reaction was monitored for 24 hr, and during the kinetic experiments, samples were collected at several reaction times and analyzed by HPLC-UV-PAD. In the degradation process, eleven different compounds (intermediate and by-products) were detected, among them the metabolites 3-phenoxybenzoic acid and 3-phenoxybenzaldehyde. HPLC-UV-PAD proved to be a valuable analytical technique for the rapid and reliable separation and determination of esfenvalerate, its degradation intermediates, and by-products.

Electrochemical behavior of parent and photodegradation products of some selected pesticides

Electrochemical behavior of pesticides is extensively studied, but little attention has been given to the study of their degradation products (by-products) by electrochemical methods. However, the degradation products of pesticides can be even more toxic then the parent products and such studies should be encouraged. Therefore, the objective of this work was to evaluate the electroactivity of by-products of imazaquin, methylparathion, bentazon and atrazine, generated by UV irradiation and measured using cyclic and differential pulse voltammetry and UV-visible absorption spectrophotometry. Results have shown that several by-products exhibit electroactivity, allowing, in some cases, the simultaneous determination of both parent and degradation products.

Photo-fenton degradation of poly(Ethyleneglycol)

Polyethyleneglycol (PEG) was photooxidized in a photo-Fenton system and results compared with the dark reaction. The products were analysed using GPC and HPLC. In the absence of light, PEG samples needed 490 min to reduce their w by 50%, whereas under UV irradiation, only 10 min were necessary. The exponential decay of w with a concomitant increase in polydispersity and number of average chain scission, characterized a random chain scission mechanism. The degradation products of PEG in both systems showed the presence of lower molecular weight products, including smaller ethyleneglycols and formic acid. The mechanism involves consecutive processes, were the larger ethyleneglycols give rise, successively, to smaller ones. This suggests that the mechanism involves successive scissions of the polymer chain. Irradiated samples decomposed faster than those kept in the dark This study proves that the foto-Fenton method associated with UV-light is a good reactant for PEG photodegradation.

Relevance of extractives and wood transformation products on the biodegradation of Pinus taeda by Ceriporiopsis subvermispora

Ceriporiopsis subvermispora is a promising white-rot fungus for biopulping. However, the underlying biochemistry involved in lignin removal and insignificant cellulose degradation by this species is not completely understood. This paper addresses this topic focusing on the involvement of ethanol-soluble extractives and wood transformation products in the biodegradation process. Cultures containing ethanol-extracted or in natura wood chips presented similar levels of extracellular enzymes and degradation of wood components. Fe3+-reducing compounds present in undecayed Pinus taeda were rapidly diminished by fungal degradation. Lignin-degradation products released during biodegradation restored part of the Fe3+-reducing activity. However, Fe3+ reduction was ineffective in presence of 0.5 mM oxalate at pH 4.5. Fungal consumption of Fe3+-reducing compounds and secretion of oxalic acid minimized the significance of Fenton`s reaction in the initial stages of wood biotreatment. This would explain limited polysaccharide degradation by the fungus that also lacks a complete set of hydrolytic enzymes. Scientific relevance of the paper: Ceriporiopsis subvermispora is a white-rot fungus suitable for biopulping processes because it degrades lignin selectively and causes significant structural changes on the wood components during the earlier decay stages. However, the intricate mechanism to explain lignin transformation and insignificant cellulose degradation by this species remains poorly understood. Some recent evidences pointed out for lipid peroxidation reactions as all initiating process explaining lignin degradation. On the other hand, alkylitaconic acids produced by the fungus via transformations of fatty acids occurring in wood showed to prevent polysaccharide degradation in Fenton reactions. In this context, one may conclude that the involvement of native wood substances or their transformation products in the overall wood biodegradation process induced by C subvermispora is still a matter of discussion. While free and esterified fatty acids present in wood extractives may be involved in the biosynthesis of alkylitaconic acids and in lipid peroxidation reactions, some extractives and lignin degradation products can reduce Fe3+, providing Fe2+ species needed to form OH radical via Fenton`s reaction. The present study focuses on this topic by evaluating the relevance of ethanol-soluble extractives and wood transformation products on the biodegradation of P. taeda by C subvermispora. For this, solid-state cultures containing ethanol-extracted and in natura wood chips were evaluated in details for up to 4 weeks. (C) 2007 Elsevier Ltd. All rights reserved.

Analysis of Intracellular Substrates and Products of Thimet Oligopeptidase in Human Embryonic Kidney 293 Cells

Thimet oligopeptidase (EC 3.4.24.15; EP24.15) is an intracellular enzyme that has been proposed to metabolize peptides within cells, thereby affecting antigen presentation and G protein-coupled receptor signal transduction. However, only a small number of intracellular substrates of EP24.15 have been reported previously. Here we have identified over 100 peptides in human embryonic kidney 293 (HEK293) cells that are derived from intracellular proteins; many but not all of these peptides are substrates or products of EP24.15. First, cellular peptides were extracted from HEK293 cells and incubated in vitro with purified EP24.15. Then the peptides were labeled with isotopic tags and analyzed by mass spectrometry to obtain quantitative data on the extent of cleavage. A related series of experiments tested the effect of overexpression of EP24.15 on the cellular levels of peptides in HEK293 cells. Finally, synthetic peptides that corresponded to 10 of the cellular peptides were incubated with purified EP24.15 in vitro, and the cleavage was monitored by high pressure liquid chromatography and mass spectrometry. Many of the EP24.15 substrates identified by these approaches are 9-11 amino acids in length, supporting the proposal that EP24.15 can function in the degradation of peptides that could be used for antigen presentation. However, EP24.15 also converts some peptides into products that are 8-10 amino acids, thus contributing to the formation of peptides for antigen presentation. In addition, the intracellular peptides described here are potential candidates to regulate protein interactions within cells.

Monitoring time-dependent degradation of phospholipids in sectioned tissues by MALDI imaging mass spectrometry.

Imaging mass spectrometry (IMS) is useful for visualizing the localization of phospholipids on biological tissue surfaces creating great opportunities for IMS in lipidomic investigations. With advancements in IMS of lipids, there is a demand for large-scale tissue studies necessitating stable, efficient and well-defined sample handling procedures. Our work within this article shows the effects of different storage conditions on the phospholipid composition of sectioned tissues from mouse organs. We have taken serial sections from mouse brain, kidney and liver thaw mounted unto ITO-coated glass slides and stored them under various conditions later analyzing them at fixed time points. A global decrease in phospholipid signal intensity is shown to occur and to be a function of time and temperature. Contrary to the global decrease, oxidized phospholipid and lysophospholipid species are found to increase within 2 h and 24 h, respectively, when mounted sections are kept at ambient room conditions. Imaging experiments reveal that degradation products increase globally across the tissue. Degradation is shown to be inhibited by cold temperatures, with sample integrity maintained up to a week after storage in −80 °C freezer under N2 atmosphere. Overall, the results demonstrate a timeline of the effects of lipid degradation specific to sectioned tissues and provide several lipid species which can serve as markers of degradation. Importantly, the timeline demonstrates oxidative sample degradation begins appearing within the normal timescale of IMS sample preparation of lipids (i.e. 1-2 h) and that long-term degradation is global. Taken together, these results strengthen the notion that standardized procedures are required for phospholipid IMS of large sample sets, or in studies where many serial sections are prepared together but analyzed over time such as in 3-D IMS reconstruction experiments.

The evaluation of hazardous gas components caused by the thermal degradation of plant oils and animal fats

Neste Oil has introduced plant oils and animal fats for the production of NExBTL renewable diesel, and these raw materials differ from the conventional mineral based oils. One subject of new raw materials study is thermal degradation, or in another name pyrolysis, of these organic oils and fats. The aim of this master’s thesis is to increase knowledge on thermal degradation of these new raw materials, and to identify possible gaseous harmful thermal degradation compounds. Another aim is to de-termine the health and environmental hazards of identified compounds. One objective is also to examine the formation possibilities of hazardous compounds in the produc-tion of NExBTL-diesel. Plant oils and animal fats consist mostly of triglycerides. Pyrolysis of triglycerides is a complex phenomenon, and many degradation products can be formed. Based on the literature studies, 13 hazardous degradation products were identified, one of which was acrolein. This compound is very toxic and dangerous to the environment. Own pyrolysis experiments were carried out with rapeseed and palm oils, and with a mix-ture of palm oil and animal fat. At least 12 hazardous compounds, including acrolein, were analysed from the gas phase. According to the experiments, the factors which influence on acrolein formation are the time of the experiment, the sphere (air/hydrogen) in which the experiment is carried out, and the characteristics of the used oil. The production of NExBTL-diesel is not based on pyrolysis. This is why thermal degradation is possible only when abnormal process conditions prevail.

Electrochemical behavior of parent and photodegradation products of some selected pesticides

Electrochemical behavior of pesticides is extensively studied, but little attention has been given to the study of their degradation products (by-products) by electrochemical methods. However, the degradation products of pesticides can be even more toxic then the parent products and such studies should be encouraged. Therefore, the objective of this work was to evaluate the electroactivity of by-products of imazaquin, methylparathion, bentazon and atrazine, generated by UV irradiation and measured using cyclic and differential pulse voltammetry and UV-visible absorption spectrophotometry. Results have shown that several by-products exhibit electroactivity, allowing, in some cases, the simultaneous determination of both parent and degradation products.

Colonic metabolism of dietary polyphenols: influence of structure on microbial fermentation products

The metabolism of chlorogenic acid., naringin, and rutin, representative members of three common families of dietary polyphenols, the hydroxycinnamates, the flavanones, and the flavonols, respectively, was studied in an in vitro mixed culture model of the human colonic microflora. Time- and concentration-dependent degradation of all three compounds was observed, which was associated with the following metabolic events after cleavage of the ester or glycosidic bond: reduction of the aliphatic double bond of the resulting hydroxycinnamate caffeic acid residue; dehydroxylation and ring fission of the heterocyclic C-ring of the resulting deglycosylated flavanone, naringenin, and of the deglycosylated flavonol, quercetin (which differed depending on the substitution). The metabolic events, their sequences, and major phenolic end products, as identified by GC-MS or LC-MS/MS, were elucidated from the structural characteristics of the investigated compounds. The major phenolic end products identified were 3-D-hydroxyphenyl)propionic acid for chlorogenic acid, 3-(4-hydroxyphenyl)-propionic acid and 3-phenylpropionic acid for naringin, and 3-hydroxyphenylacetic acid and 3-(3-hydroxyphenyl)-propionic acid for rutin. The degree of degradation of the compounds studied was significantly influenced by the substrate concentration as well as individual variations in the composition of the fecal flora. The results support extensive metabolism of dietary polyphenols in the colon, depending on substrate concentration and residence time, with resultant formation of simple phenolics, which can be considered biomarkers of colonic metabolism if subsequently absorbed. It is also apparent that a relatively small number of phenolic degradation products are formed in the colon from the diverse group of natural polyphenols. (C) 2003 Elsevier Inc. All rights reserved.

Effect of molecule branching and glycosidic linkage on the degradation of polydextrose by gut microbiota.

Polydextrose is a randomly linked complex glucose oligomer that is widely used as a sugar replacer, bulking agent, dietary fiber and prebiotic. Polydextrose is poorly utilized by the host and, during gastrointestinal transit, it is slowly degraded by intestinal microbes, although it is not known which parts of the complex molecule are preferred by the microbes. The microbial degradation of polydextrose was assessed by using a simulated model of colonic fermentation. The degradation products and their glycosidic linkages were measured by combined gas chromatography and mass spectrometry, and compared to those of intact polydextrose. Fermentation resulted in an increase in the relative abundance of non-branched molecules with a concomitant decrease in single-branched glucose molecules and a reduced total number of branching points. A detailed analysis showed a preponderance of 1,6 pyranose linkages. The results of this study demonstrate how intestinal microbes selectively degrade polydextrose, and provide an insight into the preferences of gut microbiota in the presence of different glycosidic linkages.

Glucosinolates, myrosinase hydrolysis products, and flavonols found in rocket (Eruca sativa and Diplotaxis tenuifolia)

Rocket species have been shown to have very high concentrations of glucosinolates and flavonols, which have numerous positive health benefits with regular consumption. In this review we highlight how breeders and processors of rocket species can utilize genomic and phytochemical research to improve varieties and enhance the nutritive benefits to consumers. Plant breeders are increasingly looking to new technologies such as HPLC, UPLC, LC-MS and GC-MS to screen populations for their phytochemical content to inform plant selections. Here we collate the research that has been conducted to-date in rocket, and summarise all glucosinolate and flavonol compounds identified in the species. We emphasize the importance of the broad screening of populations for phytochemicals and myrosinase degradation products, as well as unique traits that may be found in underutilized gene bank resources. We also stress that collaboration with industrial partners is becoming essential for long-term plant breeding goals through research.

Surfactant degradation by a catechol-driven Fenton reaction

The addition of 0.5 mM catechol is shown to accelerate the degradation and mineralization of the anionic surfactant DOWFaX (TM) 2A1 (sodium dodecyldiphenyloxide disulfonate) under conventional Fenton reaction conditions (Fe(II) plus H(2)O(2) at pH 3). The catalytic effect causes a 3-fold increase in the initial rate (up to ca. 20 min) of conversion of the surfactant to oxidation products (apparent first-order rate constants of 0.021 and 0.061 min(-1) in the absence and presence of catechol, respectively). Although this catalytic rate increase persists for a certain amount of time after complete disappearance of catechol itself (ca. 8 min), the reaction rate begins to decline slowly after the initial 20 min towards that observed in the absence of added catechol. Total organic carbon (TOC) measurements of net mineralization and cyclic voltammetric and high performance liquid chromatographic (HPLC) measurements of the initial rate of reaction of catechol and the surfactant provide insight into the role of catechol in promoting the degradation of the surfactant and of degradation products as the eventual inhibitors of the Fenton reaction. (C) 2010 Elsevier B.V. All rights reserved.

Photochemical degradation of 2,4-D and atrazine in well-defined media

Atrazine and 2,4-D are common herbicides used for crop, lawn, and rangeland management. Photochemical degradation has been proposed as one safe and efficient remediation strategy for both 2,4-D and Atrazine. In the presence of iron(llI) and hydrogen peroxide these herbicides decay by both thermal and light induced oxidation. Past studies have focused primarily on sun light as an energy source. This work provides a mechanistic description of herbicide degradation incorporating intermediate degradation products produced in the dark and under well-defined light conditions.