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.

Thermal degradation of a brominated bisphenol a derivative

The thermal degradation of 2,6,2',6'-tetrabromo-4,4-pm-isoproylidene-di phenol (tetrabromobisphenol A) (TBBPA) has been investigated and a mechanism for its thermal degradation is suggested. TBBPA is a comonomer widely used in epoxy and in unsaturated polyester resins to impart fire retardance. These resins find a common use in electric and electronic equipment. The presence of bromine atoms is the key factor in fire retardant activity, while on the other hand it represents an ecological problem when pyrolytic recycling is programmed at the end of the useful life of such items. However, pyrolysis is the more advantageous recycling system for thermosetting resins and thus efforts should be made to control the pyrolysis in order to avoid or minimize the development of toxics. Homolytic scission of the aromatic bromine and condensation of aromatic bromine with phenolic hydroxyl are the main processes occuring in the range 270-340°C. A large amount of charred residue is left as a consequence of condensation reactions. HBr and brominated phenols and bisphenols are the main volatile products formed. Brominated dibenzodioxins structures are included in the charred residue and not evolved in the volatile phases.

Effect of sample preparation on the thermal degradation of metal-added biomass

The present study investigates the effect of different sample preparation methods on the pyrolysis behaviour of metal-added biomass; Willow samples were compared in the presence of two salts of zinc and lead containing sulphate and nitrate anions which were added to the wood samples with three different techniques as dry-mixing, impregnation and ion-exchange. The effect of acid and water wash as common demineralisation pre-treatments were also analysed to evaluate their roles in the thermal degradation of the biomass. Results from thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and pyrolysis-mass spectrometry (Py-MS) measurements indicated that these pre-treatments change the matrix and the physical-chemical properties of wood. Results suggested that these structural changes increase the thermal stability of cellulose during pyrolysis. Sample preparation was also found to be a crucial factor during pyrolysis; different anions of metal salts changed the weight loss rate curves of wood material, which indicates changes in the primary degradation process of the biomass. Results also showed that dry-mixing, impregnation or ion-exchange influence the thermal behaviour of wood in different ways when a chosen metal salt was and added to the wood material. © 2011 Elsevier B.V. All rights reserved.

The effect of a curing agent on the thermal degradation of fire retardant brominated epoxy resins

The diglycidyl ether of tetrabromobisphenol A, the diglycidyl ether of bisphenol A and their mixture was cured by 4,4'-diaminodiphenyl methane. The pyrolysis of the obtained epoxy resins was studied by TG, DSC, TG/FTIR as well as FTIR characterization of pyrolysis residues. The gaseous and high boiling pyrolysis products were collected, characterized by GC/MS and their formation is discussed. The brominated epoxy resins are thermally less stable than the non-brominated ones. This effect is caused by the amine-containing hardener. The degradation initiation reaction is associated with the formation of hydrogen bromide which further destabilizes the epoxy network. The effect of the curing agent can be used in recycling of epoxy resins to separate brominated pyrolysis products from non-brominated ones.

Skeletal muscle atrophy, a link between depression of protein synthesis and increase in degradation

Both proteolysis-inducing factor (PIF) and angiotensin II have been shown to produce a depression in protein synthesis in murine myotubes concomitant with an increased phosphorylation of eukaryotic initiation factor 2 (eIF2α). Both PIF and angiotensin II were shown to induce autophosphorylation of the RNA-dependent protein kinase (PKR), and an inhibitor of this enzyme completely attenuated the depression in protein synthesis and prevented the induction of eIF2α phosphorylation. The PKR inhibitor also completely attenuated the increase in protein degradation induced by PIF and angiotensin II and prevented the increase in proteasome expression and activity. To confirm these results myotubes were transfected with plasmids that express either wild-type PKR, or a catalytically inactive PKR variant, PKRΔ6. Myotubes expressing PKRΔ6 showed no increase in eIF2α phosphorylation in response to PIF or angiotensin II, no depression in protein synthesis, and no increase in protein degradation or increase in proteasome expression. Induction of the ubiquitin-proteasome pathway by PIF and angiotensin II has been linked to activation of the transcription factor nuclear factor-κB (NF-κB). Inhibition of PKR prevented nuclear migration of NF-κB in response to both PIF and angiotensin II, by preventing degradation of the inhibitor protein I-κB. Phosphorylation of PKR and eIF2α was also significantly increased in the gastrocnemius muscle of weight losing mice bearing the MAC16 tumor, suggesting that a similar process may be operative in cancer cachexia. These results provide a link between the depression of protein synthesis in skeletal muscle and the increase in protein degradation. © 2007 by The American Society for Biochemistry and Molecular Biology, Inc.

Characterisation and oxidative stability of speciality plant seed oils

The past decade has seen an influx of speciality plant seed oils arriving into the market place. The need to characterise these oils has become an important aspect of the oil industry. The characterisation of the oils allows for the physical and chemical properties of the oil to be determined. Speciality oils were characterised based on their lipid and fatty acid profiles and categorised as monounsaturated rich (oleic acid as the major acyl components e.g. Moringa and Marula oil), linoleic acid rich (Grape seed and Evening Primrose oil) or linolenic acid rich (Flaxseed and Kiwi oil). The quality of the oils was evaluated by determining the free fatty acid content, the peroxide value (that measures initial oxidation) and p-anisidine values (that determines secondary oxidation products containing the carbonyl function). A reference database was constructed for the oils in order to compare batches of oils for their overall quality including oxidative stability. For some of the speciality oils, the stereochemistry of the triacylglycerols was determined. Calophyllum, Coffee, Poppy and Sea Buckthorn oils stereochemistry was determined. The oils were enriched with saturated and/or a monounsaturated fatty acids at position sn-1 and sn-3. The sn-2 position of the four oils was esterified with a polyunsaturated and/or a monounsaturated fatty acid indicating that they follow a typical acylation pathway and no novel acylation activity was evident from these studies (e.g enrichment of saturates at the sn-2 position). The oxidative stability of the oils was evaluated at 18oC and 60oC and the effect of adding a-tocopherol at commercially used level i.e 750ppm was assessed. The addition of 750ppm of a-tocopherol at 18oC increased the oxidative stability of Brown flax, Moringa, Wheat germ and Yangu oils. At 60oC Brown Flax, Manketti and Pomegranate oil polymerised after 48 hours. The addition of 750ppm a-tocopherol delayed the onset of polymerisation by up to 48 hours in Brown Flax seed oil. Pomegranate oil showed a high resistance to oxidation, and was blended into other speciality oils at 1%. Pomegranate oil increased the oxidative stability of Yangu oil at 18oC. The addition of Pomegranate oil to Wheat germ oil at 60oC, decreased the peroxide content by 10%. In Manketti and Brown Flaxseed oil at elevated temperatures, Pomegranate oil delayed the onset of polymerisation. Preliminary studies of Pomegranate oil blending to Moringa and Borage oil showed it to be more effective than a-tocopherol for certain oils. The antioxidant effects observed following the addition of Pomegranate oil may be due to its conjugated linolenic acid fatty acid, punicic acid.

Optic sensors of high refractive-index responsivity and low thermal cross sensitivity that use fiber Bragg gratings of >80° tilted structures

For the first time to the authors' knowledge, fiber Bragg gratings (FBGs) with >80° tilted structures have been fabricated and characterized. Their performance in sensing temperature, strain, and the surrounding medium's refractive index was investigated. In comparison with normal FBGs and long-period gratings (LPGs), >80° tilted FBGs exhibit significantly higher refractive-index responsivity and lower thermal cross sensitivity. When the grating sensor was used to detect changes in refractive index, a responsivity as high as 340nm/refractive-index unit near an index of 1.33 was demonstrated, which is three times higher than that of conventional LPGs.

Modulation of sarcoplasmic/endoplasmic reticulum Ca(2+)-ATPase activity and oxidative modification during the development of adjuvant arthritis

Adjuvant arthritis (AA) was induced by intradermal administration of Mycobacterium butyricum to the tail of Lewis rats. In sarcoplasmic reticulum (SR) of skeletal muscles, we investigated the development of AA. SR Ca(2+)-ATPase (SERCA) activity decreased on day 21, suggesting possible conformational changes in the transmembrane part of the enzyme, especially at the site of the calcium binding transmembrane part. These events were associated with an increased level of protein carbonyls, a decrease in cysteine SH groups, and alterations in SR membrane fluidity. There was no alteration in the nucleotide binding site at any time point of AA, as detected by a FITC fluorescence marker. Some changes observed on day 21 appeared to be reversible, as indicated by SERCA activity, cysteine SH groups, SR membrane fluidity, protein carbonyl content and fluorescence of an NCD-4 marker specific for the calcium binding site. The reversibility may represent adaptive mechanisms of AA, induced by higher relative expression of SERCA, oxidation of cysteine, nitration of tyrosine and presence of acidic phospholipids such as phosphatidic acid. Nitric oxide may regulate cytoplasmic Ca(2+) level through conformational alterations of SERCA, and decreasing levels of calsequestrin in SR may also play regulatory role in SERCA activity and expression.

Intermediate pyrolysis studies of aquatic biomass and potential applications in the BtVB-process

Aquatic biomass is seen as one of the major feedstocks to overcome difficulties associated with 1st generation biofuels, such as competition with food production, change of land use and further environmental issues. Although, this finding is widely accepted only little work has been carried out to investigate thermo-chemical conversion of algal specimen to produce biofuels, power and heat. This work aims at contributing fundamental knowledge for thermo-chemical processing of aquatic biomass via intermediate pyrolysis. Therefore, it was necessary to install and commission an analytical pyrolysis apparatus which facilitates intermediate pyrolysis process conditions as well as subsequent separation and detection of pyrolysates (Py- GC/MS). In addition, a methodology was established to analyse aquatic biomass under intermediate conditions by Thermo-Gravimetric Analysis (TGA). Several microalgae (e.g. Chlamydomonas reinhardtii, Chlorella vulgaris) and macroalgae specimen (e.g. Fucus vesiculosus) from main algal divisions and various natural habitats (fresh and saline water, temperate and polar climates) were chosen and their thermal degradation under intermediate pyrolysis conditions was studied. In addition, it was of interest to examine the contribution of biochemical constituents of algal biomass onto the chemical compounds contained in pyrolysates. Therefore, lipid and protein fractions were extracted from microalgae biomass and analysed separately. Furthermore, investigations of residual algal materials obtained by extraction of high valuable compounds (e.g. lipids, proteins, enzymes) were included to evaluate their potential for intermediate pyrolysis processing. On basis of these thermal degradation studies, possible applications of algal biomass and from there derived materials in the Bio-thermal Valorisation of Biomass-process (BtVB-process) are presented. It was of interest to evaluate the combination of the production of high valuable products and bioenergy generation derived by micro- and macro algal biomass.

Optic sensors of high refractive-index responsivity and low thermal cross sensitivity that use fiber Bragg gratings of >80° tilted structures

For the first time to the authors' knowledge, fiber Bragg gratings (FBGs) with >80° tilted structures nave been fabricated and characterized. Their performance in sensing temperature, strain, and the surrounding medium's refractive index was investigated. In comparison with normal FBGs and long-period gratings (LPGs), >80° tilted FBGs exhibit significantly higher refractive-index responsivity and lower thermal cross sensitivity. When the grating sensor was used to detect changes in refractive index, a responsivity as high as 340 nm/refractive-index unit near an index of 1.33 was demonstrated, which is three times higher than that of conventional LPGs. © 2006 Optical Society of America.

Revealing 4-hydroxynonenal-histidine adducts as qualitative and quantitative biomarker of oxidative stress, lipid peroxidation and oxidative homeostasis

Findings on growth regulating activities of the end-product of lipid peroxidation 4-hydroxy-2-nonenal (HNE), which acts as a “second messenger of free radicals”, overlapped with the development of antibodies specific for the aldehyde-protein adducts. These led to qualitative immunochemical determinations of the HNE presence in various pathophysiological processes and to the change of consideration of the aldehyde’s bioactivities from toxicity into cell signalling. Moreover, findings of the HNE-protein adduct in various organs under physiological circumstances support the concept of “oxidative homeostasis”, which implies that oxidative stress and lipid peroxidation are not only pathological but also physiological processes. Reactive aldehydes, at least HNE, could play important role in oxidative homeostasis, while complementary research approaches might reveal the relevance of the aldehydic-protein adducts as major biomarkers of oxidative stress, lipid peroxidation and oxidative homeostasis. Aiming to join efforts in such research activities researchers interacting through the International 4-Hydroxynonenal Club acting within the SFRR-International and through networking projects of the system of the European Cooperation in Science and Technology (COST) carried validation of the methods for lipid peroxidation and further developed the genuine 4-HNE-His ELISA founding quantitative and qualitative methods for detection of 4-HNE-His adducts as valuable tool to study oxidative stress and lipid peroxidation in cell cultures, various organs and tissues and eventually for human plasma and serum analyses [1]. Reference: 1. Weber, Daniela. Lidija, Milkovic. Measurement of HNE-protein adducts in human plasma and serum by ELISA—Comparison of two primary antibodies. Redox Biol. 2013. 226-233.

Melamine phosphate as a component of intumescent coatings

Melamine orthophosphate has been shown to exhibit variations in its chemical constitution, and crystal shape and size, dependent upon the method of production. These crystal types have been incorporated with epoxy resin to produce intumescent coatings, which have been tested on a small scale fire testing device, designed and calibrated within this project. The factors influencing performance in three fire test regimes are the percentage loading of melamine phosphate, its chemical constitution, crystal size and shape, thermal degradation, and state of agglomeration . and dispersion in the coating, determined by the method of incorporation into the coating. When melamine phosphate is heat treated at 210ºC, a process designed to reduce its solubility, the performance of coatings produced with such material is profoundly affected, depending mainly on crystal size and shape alone. Consideration of heat transfer across the chars produced has allowed a quantitative evaluation of the thermal resistance of chars throughout a test. An optimum production route for melamine phosphate has been suggested, taking into account the requirements for weatherability of coatings as well as performance in a fire.

Metallocene ethylene-1-octene copolymers:influence of comonomer content on thermo-mechanical, rheological, and thermo-oxidative behaviours before and after melt processing in an internal mixer

The influence of the comonomer content in a series of metallocene-based ethylene-1-octene copolymers (m-LLDPE) on thermo-mechanical, rheological, and thermo-oxidative behaviours during melt processing were examined using a range of characterisation techniques. The amount of branching was calculated from 13C NMR and studies using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were employed to determine the effect of short chain branching (SCB, comonomer content) on thermal and mechanical characteristics of the polymer. The effect of melt processing at different temperatures on the thermo-oxidative behaviour of the polymers was investigated by examining the changes in rheological properties, using both melt flow and capillary rheometry, and the evolution of oxidation products during processing using infrared spectroscopy. The results show that the comonomer content and catalyst type greatly affect thermal, mechanical and oxidative behaviour of the polymers. For the metallocene polymer series, it was shown from both DSC and DMA that (i) crystallinity and melting temperatures decreased linearly with comonomer content, (ii) the intensity of the ß-transition increased, and (iii) the position of the tan δmax peak corresponding to the a-transition shifted to lower temperatures, with higher comonomer content. In contrast, a corresponding Ziegler polymer containing the same level of SCB as in one of the m-LLDPE polymers, showed different characteristics due to its more heterogeneous nature: higher elongational viscosity, and a double melting peak with broader intensity that occurred at higher temperature (from DSC endotherm) indicating a much broader short chain branch distribution. The thermo-oxidative behaviour of the polymers after melt processing was similarly influenced by the comonomer content. Rheological characteristics and changes in concentrations of carbonyl and the different unsaturated groups, particularly vinyl, vinylidene and trans-vinylene, during processing of m-LLDPE polymers, showed that polymers with lower levels of SCB gave rise to predominantly crosslinking reactions at all processing temperatures. By contrast, chain scission reactions at higher processing temperatures became more favoured in the higher comonomer-containing polymers. Compared to its metallocene analogue, the Ziegler polymer showed a much higher degree of crosslinking at all temperatures because of the high levels of vinyl unsaturation initially present.

Synthesis and evaluation of novel polymer modifiers for biodegradable polymers

The effects of ester plasticizers and copolymers on the mechanical properties of the natural biodegradable polymers, poly(3-hydroxybutyrate) [PHB] and poly(lactic acid) [PLA] have been studied after subjecting to melt processing conditions. Ester plasticizers were synthesized from citric, tartaric and maleic acids using various alcohols. A variety of PLA copolymers have also been prepared from poly(ethylene glycol) derivatives using stannous octanoate catalysed ring opening polymerisations of DL-lactide. A novel PLA star copolymer was also prepared from an ethoxylated pentaerythritol. The structures of these copolymers were determined by NMR spectroscopy. The plasticizing effect of the synthesised additives at various concentrations was determined. While certain additives were capable of improving the mechanical properties of PLA, none were effective in PHB. Moreover, it was found that certain combinations of additives exhibited synergistic effects. Possible mechanisms are discussed. Biotic and abiotic degradation studies showed that the plasticizers (esters and copolymers) did not inhibit the biodegradability of PHB or PLA in compost at 60°C. Simple toxicity tests carried out on compost extract and its ability to support the growth of cress seeds was established. PLA was found to be susceptible to limited thermal degradation under melt processing conditions. Conventional phenolic antioxidants showed no significant effect on this process, suggesting that degradation was not predominantly a free radical process. PLA also underwent photo-oxidative degradation with UV light and the process could be accelerated in the presence of a photoactivator such as iron (III) diisononyl dithiocarbamate. The mechanisms for the above processes are discussed. Finally, selected compounds were prepared on a pilot plant scale. Extruded and blown films were prepared containing these additives with conventional polymer processing equipment. The mechanical properties were similar to those obtained with laboratory produced compression moulded films.