Fingerprint Volatile Organic Compounds (VOC) analysis in Goat’s Milk and Halloumi Cheese as Marker for Authentication of Region of Origin

Goats’ milk is responsible for unique traditional products such as Halloumi cheese. The characteristics of Halloumi depend on the original features of the milk and on the conditions under which the milk has been produced such as feeding regime of the animals or region of production. Using a range of milk (33) and Halloumi (33) samples collected over a year from three different locations in Cyprus (A, Anogyra; K, Kofinou; P, Paphos), the potential for fingerprint VOC analysis as marker to authenticate Halloumi was investigated. This unique set up consists of an in-injector thermo desorption (VOCtrap needle) and a chromatofocusing system based on mass spectrometry (VOCscanner). The mass spectra of all the analyzed samples are treated by multivariate analysis (Principle component analysis and Discriminant functions analysis). Results showed that the highland area of product (P) is clearly identified in milks produced (discriminant score 67%). It is interesting to note that the higher similitude found on milks from regions “A” and “K” (with P being distractive; discriminant score 80%) are not ‘carried over’ on the cheeses (higher similitude between regions “A” and “P”, with “K” distinctive). Data have been broken down into three seasons. Similarly, the seasonality differences observed in different milks are not necessarily reported on the produced cheeses. This is expected due to the different VOC signatures developed in cheeses as part of the numerous biochemical changes during its elaboration compared to milk. VOC however it is an additional analytical tool that can aid in the identification of region origin in dairy products.

Do vesicle cells of the red alga Asparagopsis (Falkenbergia stage) play a role in bromocarbon production?

The Rhodophyceae (red algae) are an established source of volatile halocarbons in the marine environment. Some species in the Bonnemaisoniaceae have been reported to contain large amounts of halogens in structures referred to as vesicle cells, suggesting involvement of these specialised cells in the production of halocarbons. We have investigated the role of vesicle cells in the accumulation and metabolism of bromide in an isolate of the red macroalga Asparagopsis (Falkenbergia stage), a species known to release bromocarbons. Studies of laboratory-cultivated alga, using light microscopy, revealed a requirement of bromide for both the maintenance and formation of vesicle cells. Incubation of the alga in culture media with bromide concentrations below 64 mg l-1 (the concentration of Br- in seawater) resulted in a decrease in the proportion of vesicle cells to pericentral cells. The abundance of vesicle cells was correlated with bromide concentration below this level. Induction of vesicle cell formation in cultures of Falkenbergia occurred at concentrations as low as 8 mg l-1, with the abundance of vesicle cells increasing with bromide concentration up to around 100 mg l-1. Further studies revealed a positive correlation between the abundance of vesicle cells and dibromomethane and bromoform production. Interestingly, however, whilst dibromomethane production was stimulated by the presence of bromide in the culture media, bromoform release remained unaffected suggesting that the two compounds are formed by different mechanisms.

The limits of legitimacy: Former loyalist combatants and peace-building in Northern Ireland

The British government has a fraught relationship with former combatants in Northern Ireland. It simultaneously benefits from former combatants’ peace-building efforts, whilst denying them statutory recognition and funding. Drawing on interviews and focus groups with politically motivated former loyalist combatants and statutory representatives in Belfast, this paper explores the complex and sometimes contradictory relationship between them. It argues that that a lack of legitimacy is the biggest obstacle to good working relationships, and that positive engagement may be crucial in order to promote the implementation of peace in the most difficult to reach and volatile constituencies in Northern Ireland.

Neostigmine antagonism of rocuronium block during anesthesia with sevoflurane, isoflurane or propofol

Purpose: To examine the influence of continuing administration of sevoflurane or isoflurane during reversal of rocuronium induced neuromuscular block with neostigmine. Methods: One hundred and twenty patients, divided into three equal groups, were randomly allocated to maintenance of anesthesia with sevoflurane, isoflurane or propofol. Neuromuscular block was induced with rocuronium and monitored using train-of-four (TOF) stimulation of the ulnar nerve and recording the force of contraction of the adductor pollicis muscle. Neostigmine was administered when the first response in TOF had recovered to 25%. At this time the volatile agent administration was stopped or propofol dosage reduced in half the patients in each group (n = 20 in each group). The times to attain TOF ratio of 0.8, and the number of patients attaining this end point within 15 min were recorded. Results: The times (mean ± SD) to recovery of the TOF ratio to 0.8 were 12.0 ± 5.5 and 6.8 ± 2.3 min in the sevoflurane continued and sevoflurane stopped groups, 9.0 ± 8.3 and 5.5 ± 3.0 min in the isoflurane continued and isoflurane stopped groups, and 5.2 ± 2.8 and 4.7 ±1.5 min in the propofol continued and propofol stopped groups (P <0.5- 01). Only 9 and 15 patients in the sevoflurane and isoflurane continued groups respectively had attained a TOF ratio of 0.8 within 15 min (P <0.001 for sevoflurane). Conclusions: The continued administration of sevoflurane, and to a smaller extent isoflurane, results in delay in attaining adequate antagonism of rocuronium induced neuromuscular block.

Mutual Solubilities of Water and the [Cnmim][Tf2N] Hydrophobic Ionic Liquids

Ionic liquids (ILs) have recently garnered increased attention because of their potential environmental benefits as "green" replacements over conventional volatile organic solvents. While ILs cannot significantly volatilize and contribute to air pollution, even the most hydrophobic ones present some miscibility with water posing environmental risks to the aquatic ecosystems. Thus, the knowledge of ILs toxicity and their water solubility must be assessed before an accurate judgment of their environmental benefits and prior to their industrial applications. In this work, the mutual solubilities for [C2-C8mim][Tf2N] (n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and water between 288.15 and 318.15 K at atmospheric pressure were measured. Although these are among the most hydrophobic ionic liquids known, the solubility of water in these compounds is surprisingly large, ranging from 0.17 to 0.36 in mole fraction, while the solubility of these ILs in water is much lower ranging from 3.2 × 10-5 to 1.1 × 10-3 in mole fraction, in the temperature and pressure conditions studied. From the experimental data, the molar thermodynamic functions of solution and solvation such as Gibbs energy, enthalpy, and entropy at infinite dilution were estimated, showing that the solubility of these ILs in water is entropically driven. The predictive capability of COSMO-RS, a model based on unimolecular quantum chemistry calculations, was evaluated for the description of the binary systems investigated providing an acceptable agreement between the model predictions and the experimental data both with the temperature dependence and with the ILs structural variations.

Relationships between antioxidant activity, color, and flavor compounds of crystal malt extracts

Aqueous extracts were prepared from five barley crystal malts (color range 15-440 degrees EBC, European Brewing Convention units). Antioxidant activity was determined by using the 2,2'-azinobis(3-ethylbenothiazoline-6-sulfonic acid) (ABTS(.+)) radical cation scavenging method. Antioxidant activity increased with increasing color value although the rate of increase decreased with increasing color value. Color was measured in CIELAB space. Extracts of the 15, 23, and 72 degrees EBC malts followed the same dilution pathway as did the 148 degrees EBC sample at higher dilution levels, indicating that they could each be used to give the same color by appropriate dilution. The 440 degrees EBC sample followed a different dilution pathway, indicating that different compounds were responsible for color in this extract. Fifteen selected volatile compounds were monitored using gas chromatography/mass spectrometry (GC/MS). Levels of methylpropanal, 2-methylbutanal, and 3-methylbutanal were highest for the 72 degrees EBC sample. When odor threshold values of the selected compounds were taken into account, 3-methylbutanal was the most important contributor to flavor., Relationships between levels of the lipid oxidation products, hexanal and (E)-2-nonenal, and antioxidant activity were complex, and increasing antioxidant activity for samples in the range of 15-148 degrees EBC did-not result in reduced levels of these lipid-derived compounds. When different colored malt extracts were diluted to give the same a* and b* values, calculated antioxidant activity and amounts of 3-methylbutanal, hexanal, and (E)-2-nonenal decreased with increasing degrees EBC value.

Choice and use of standards for dynamic headspace trapping and application to the analysis of the volatiles of baked potato

When attempting to quantify the volatile components of a food isolated by dynamic headspace trapping onto an adsorbent, the analyst has to select the most appropriate compounds to use as standards and at which stage of the analysis to add them. Factors to be borne in mind include the volatility of the standard, the response of the GC detector, and whether to add the standard to the sample or to the adsorbent trap. This chapter considers the issues and describes the application of one chosen method to the quantitation of the volatile components of baked potato.

Comparison of flavor compounds of potato chips fried in palmolein and silicone fluid

The importance of the frying oil as a heat-transfer medium and as a source of flavor precursors for the formation of potato chip flavor was investigated. Potato slices were fried in palmolein or silicone fluid, and the volatile flavor compounds of the resulting chips were isolated onto Tenax and analyzed by gas chromatography-mass spectrometry. Although the heat-transfer coefficients of the oils did not differ significantly, their temperature profiles during frying were different, probably due to greater turbulence on placing potato slices in palmolein, leading to more efficient heat transfer. Levels of Strecker aldehydes and sulfides in chips fried in the two media were not significantly different, but levels of pyrazines were significantly higher in palmolein-fried chips. Amounts of 2,4-decadienal were also significantly higher in palmolein-fried chips, but there was no significant difference in hexanal levels between the samples.

Formation of Strecker aldehydes and pyrazines in a fried potato model system

Sugars and amino acids were removed from potato slices by soaking in water and ethanol. They were then infused with various combinations of sugars (glucose and/or fructose) and amino acids (asparagine, glutamine, leucine, isoleucine, phenylalanine, and/or methionine) and fried. Volatile compounds were trapped onto Tenax prior to gas chromatography-mass spectrometry. Relative amounts of compounds (relative to the internal standard) and relative yields (per mole of amino acid infused into the slices) were determined. Amounts of 10 pyrazines, 4 Strecker aldehydes, and 4 other compounds were monitored. Relative amounts and relative yields of compounds varied according to the composition of the system. For the single amino acid-glucose systems, leucine gave the highest relative amount and relative yield of its Strecker aldehyde. Asparagine and phenylalanine gave the highest total relative amount and total relative Yield, respectively, of pyrazines. In the system containing all of the amino acids and glucose, the relative amount of 3-methylbutanal was higher, whereas the amounts of the other monitored Strecker aldehydes were lower. Most of the relative amounts of individual pyrazines were lower compared to the glucose-asparagine system, whereas the total relative yield of pyrazines was lower, compared to all of the single amino acid-glucose mixtures. Addition of fructose to the mixed amino acid-glucose model system generated Strecker aldehydes and pyrazines in ratios that were more similar to those of untreated potato chips than to those from the same system but without fructose. Both the sugars and the amino acids present in potato are crucial to the development of flavor compounds in fried potato slices.

A structural and electrochemical investigation of 1-alkyl-3-methylimidazollum salts of the nitratodioxouranate(VI) anions [{UO2(NO3)(2)}(2)(mu(4)-C2O4)](2-), [UO2(NO3)(3)](-), and [UO2(NO3)(4)](2-)

The properties of the 1-butyl-3-methylimidazolium salt of the dinuclear mu(4)-(O,O,O',O'-ethane-1,2-dioato)bis[bis-(nitrato-O,O)dioxouranate(VI)] anion have been investigated using electrochemistry, single-crystal X-ray crystallography, and extended X-ray absorbance fine structure spectroscopy: the anion structures from these last two techniques are in excellent agreement with each other. Electrochemical reduction of the complex leads to the a two-electron metal-centered reduction of U(VI) to U(IV), and the production Of UO2, or a complex containing UO2. Under normal conditions, this leads to the coating of the electrode with a passivating film. The presence of volatile organic compounds in the ionic liquids 1-alkyl-3-methylimidazolium nitrate (where the 1-alkyl chain was methyl, ethyl, propyl, butyl, pentyl, hexyl, dodecyl, hexadecyl, or octadecyl) during the oxidative dissolution of uranium(IV) oxide led to the formation of a yellow precipitate. To understand the effect of the cation upon the composition and structure of the precipitates, 1-alkyl-3-methylimidazolium salts of a number of nitratodioxouranate(VI) complexes were synthesized and then analyzed using X-ray crystallography. It was demonstrated that the length of the 1-alkyl chain played an important role, not only in the composition of the complex salt, but also in the synthesis of dinuclear anions containing the bridging mu(4)-(O,O,O',O'-ethane-1,2-dioato), or oxalato, ligand, by protecting it from further oxidation.

Phase transition and decomposition temperatures, heat capacities and viscosities of pyridinium ionic liquids

Ionic liquids are organic salts with low melting points. Many of these compounds are liquid at room temperature in their pure state. Since they have negligible vapor pressure and would not contribute to air pollution, they are being intensively investigated for a variety of applications, including as solvents for reactions and separations, as non-volatile electrolytes, and as heat transfer fluids. We present melting temperatures, glass transition temperatures, decomposition temperatures, heat capacities, and viscosities for a large series of pyridinium-based ionic liquids. For comparison, we include data for several imidazolium and quaternary ammonium salts. Many of the compounds do not crystallize, but form glasses at temperatures between 188 K and 223 K. The thermal stability is largely determined by the coordinating ability of the anion, with ionic liquids made with the least coordinating anions, like bis(trifluoromethylsulfonyl)imide, having the best thermal stability. In particular, dimethylaminopyridinium bis(trifluoromethylsulfonyl)imide salts have some of the best thermal stabilities of any ionic liquid compounds investigated to date. Heat capacities increase approximately linearly with increasing molar mass, which corresponds with increasing numbers of translational, vibrational, and rotational modes. Viscosities generally increase with increasing number and length of alkyl substituents on the cation, with the pyridinium salts typically being slightly more viscous than the equivalent imidazolium compounds. (c) 2005 Elsevier Ltd. All rights reserved.

Combustible ionic liquids by design: is laboratory safety another ionic liquid myth?

The non-flammability of ionic liquids (ILs) is often highlighted as a safety advantage of ILs over volatile organic compounds (VOCs), but the fact that many ILs are not flammable themselves does not mean that they are safe to use near fire and/or heat sources; a large group of ILs ( including commercially available ILs) are combustible due to the nature of their positive heats of formation, oxygen content, and decomposition products.

Industrial applications of ionic liquids

The potential to use Ionic Liquids (ILs) as novel solvents or fluids for a diverse range of applications has become increasingly rent as researchers in academia and try respond to challenges from atmospheric emissions and disposal of many common solvents by evaluating novel reaction media. The intrinsic non-volatile nature of ILs provides an opportunity to reduce, or even completely eliminate, hazardous and toxic emissions to the atmosphere, thus providing the promise for significant environmental benefits. In synthesis and catalysis, ILs have been used as solvents (or solvents and catalysts), with the greatest current effort on using the ILs as alternatives to VOCs. In contrast, electrochemical studies hove utills'ed the fact that ILs are liquid rather than solids to provide liquid electrolytes without needing to odd an additional solvent. is overview appraiso an appraisal of potential to use ILs in industrial applications, illustrating some areas where practical uses are being developed, and how, throuqh understanding ionic liquids in a conceptuo level, new opportunities ore continuing to evolve.

Composites of poly(ε-caprolactone) and Mo6S3I6 Nanowires

Composites of poly(e-caprolactone) (PCL) and molybdenum sulfur iodine (MoSI) nanowires were prepared using twin-screw extrusion. Extensive microscopic examination of the composites revealed the nanowires were well dispersed in the PCL matrix, although bundles of Mo6S3I6 ropes were evident at higher loadings. Secondary electron imaging (SEI) showed the nanowires had formed an extensive network throughout the PCL matrix, resulting in increased electrical conductivity of PCL, by eight orders of magnitude, and an electrical percolation threshold of 6.5T10S3vol%. Thermal analysis (DSC), WAXD, and hot stage polarized optical microscopy (HSPOM) experiments revealed Mo6S3I6 addition altered PCL crystallization kinetics, nucleation density, and crystalline content. A greater number of smaller spherulites were formed via heterogeneous nucleation. The onset of thermal decomposition (TGA) of PCL decreased by 70-C, a consequence of the thermal degradation of Mo6S3I6 to MoO3, which in turn accelerates the formation of volatile gases during the first stage of PCL decomposition.

The effect of feedstock cost on biofuel cost as exemplified by biomethane production from grass silage.

Abstract: The potential variance in feedstock costs can have signifi cant implications for the cost of a biofuel and the fi nancial viability of a biofuel facility. This paper employs the Grange Feed Costing Model to assess the cost of on-farm biomethane production using grass silages produced under a range of management scenarios. These costs were compared with the cost of wheat grain and sugarbeet roots for ethanol production at an industrial scale. Of the three feedstocks examined, grass silage represents the cheapest feedstock per GJ of biofuel produced. At a production cost of €27/tonne (t) feedstock (or €150/t volatile solids (VS)), the feedstock production cost of grass silage per gigajoule (GJ) of biofuel (€12.27) is lower than that of sugarbeet (€16.82) and wheat grain (€18.61). Grass biomethane is also the cheapest biofuel when grass silage is costed at the bottom quartile purchase price of silage of €19/t (€93/t VS). However, when considering the production costs (full-costing) of the three feedstocks, the total cost of grass biomethane (€32.37/GJ of biofuel; intensive 2-cut system) from a small on-farm facility ranks between that of sugarbeet (€29.62) and wheat grain ethanol (€34.31) produced in large industrial facilities. The feedstock costs for the above three biofuels represent 0.38, 0.57, and 0.54 of the total biofuel cost. The importance of feedstock cost on biofuel cost is further highlighted by the 0.43 increase in the cost of biomethane when grass silage is priced at the top quartile (€46/t or €232/t VS) compared to the bottom quartile purchase price.