Polycyclic aromatic hydrocarbons (PAHS) (I): Toxicity, population exposure and involved foods

Food is one of the main exogenous sources of genotoxic compounds. In heated food products, polycyclic aromatic hydrocarbons (PAHs) represent a priority group of genotoxic, mutagenic and/or carcinogenic chemical pollutants with adverse long-term health effects. People can be exposed to these compounds through different environments and via various routes: inhalation, ingestion of foods and water and even percutaneously. The presence of these compounds in food may be due to environmental contamination, to industrial handling and processing of foods and to oil processing and refining. The highest levels of these compounds are found in smoked foods, in seafood which is found in polluted waters, in grilled meats and, to a lesser extent, in vegetable fats and oils. Lower levels of PAHs are found in vegetables and in cereals and its products.

Polycyclic aromatic hydrocarbons (PAHS) (I): Measures of prevention and control

Measures of prevention and control against polycyclic aromatic hydrocarbons (PAHs) focus on an official food control, a code of best practice to reduce PAHs levels by controlling industry and in the development of a chemopreventive strategy. Regulation (EU) 835/2011 establishes maximum levels of PAHs for each food group. In addition, Regulations (EU) 333/2007 and 836/2011 set up the methods of sampling and analysis for its official control. Scientific studies prove that the chemopreventive strategy is effective against these genotoxic compounds effects. Most chemopreventive compounds studied with proven protective effects against PAHs are found in fruit and vegetables.

Deactivation of Oxidation Catalysts by Oil-Derived Sulphur

The most common mode of deactivation suffered by catalysts fitted to two-stroke engines has traditionally been thermal degradation, or even meltdown, of the washcoat and substrate. The high temperatures experienced by these catalysts are caused by excessively high concentrations of HC and CO in the exhaust gas which are, in turn, caused by a rich AFR and the loss of neat fuel to the exhaust during the scavenging period. The effects of catalyst poisoning due to additives in the oil is often regarded as a secondary, or even negligible, deactivating mechanism in two-stroke catalysts and has therefore received little attention. However, with the introduction of direct in-cylinder fuel injection to some larger versions of this engine, the quantities of HC escaping to the exhaust can be reduced to levels similar to those found on four-stroke gasoline engines. Under these conditions, the effects of poisoning are much more significant to catalyst durability, particularly for crankcase scavenged derivatives which allow considerable quantities of oil to escape into the exhaust in a neat, or partially burned form. In this paper the effects of oil-derived sulphur on catalyst performance are examined using specialised test apparatus. The oil used throughout the study was formulated specifically for a two-stroke engine fitted with direct in-cylinder fuel injection. The sulphur content of this oil was 0.21% by mass and particular attention was paid to the role of this element in the resulting deactivation. The catalyst was also designed for two-stroke applications and contained a high palladium loading of 300g/ft3 (28g/l) to prolong the life of the catalyst. It was found that the sulphur caused permanent deactivation of the CO reaction and increased the light-off temperature by around 40oC after oiling for 60 hours. This deactivation was progressive and led to a reduction in surface area of the washcoat, particularly in the micropores of around 5Å diameter. By using a validated catalyst model the change in surface area of the precious metal was estimated. It was found that the simulated palladium surface area had to be reduced by a factor of around 7.5 to produce the light-off temperature of the deactivated catalyst. Conversely, the light-off temperature of the C3H6 reaction was barely affected by the deactivation.

An insight into alkali promotion: a density functional theory study of CO dissociation on K/Rh(111)

The important role of alkali additives in heterogeneous catalysis is, to a large extent, related to the high promotion effect they have on many fundamental reactions. The wide application of alkali additives in industry does not, however, reflect a thorough understanding of the mechanism of their promotional abilities. To investigate the physical origin of the alkali promotion effect, we have studied CO dissociation on clean Rh(111) and K-covered Rh(111) surfaces using density functional theory. By varying the position of potassium atoms relative to a dissociating CO, we have mapped out the importance of different K effects on the CO dissociation reactions. The K-induced changes in the reaction pathways and reaction barriers have been determined; in particular, a large reduction of the CO dissociation barrier has been identified. A thorough analysis of this promotion effect allows us to rationalize both the electronic and the geometrical factors that govern alkali promotion effect: (i) The extent of barrier reductions depends strongly on how close K is to the dissociating CO. (ii) Direct K-O bonding that is in a very short range plays a crucial role in reducing the barrier. (iii) K can have a rather long-range effect on the TS structure, which could reduce slightly the barriers.

Reactions of polycarbonate with cyclohexene oxide and phosphites: A density functional study

Epoxides and phosphites are often used as additives to stabilize the properties of polymers, including bisphenol A polycarbonate (BPA-PC). We describe density functional (DF) calculations of the reactions of cyclohexene oxide (CHO, cyclohexane epoxide) and phosphites with chain segments of BPA-PC, with the aim of identifying possible reaction paths and energy barriers. The reactions of CHO with the OH-terminated PC chains and with the carbonate group are exothermic, although there is an energy barrier in each case of more than 10 kcal/mol. A comparison of results for different CHO isomers demonstrates the importance of steric effects. The reactions between the same groups of the PC chain and the phosphites 2-[2,4-bis(tert-butyl)phenoxy]-5,5-dimethyl-1,3,2-dioxaphosphorinane] (BPDD) and trimethyl phosphite (TMP), and their phosphonate isomers are characterized by large energy barriers.

Deposition and depletion of five anticoccidials in eggs

Anticoccidials are compounds that are widely used as feed additives to prevent and treat coccidiosis. They are licensed for use in a prescribed concentration and during a certain time interval for broilers and pullets but not for laying hens. It was shown in the past that carry-over at the feeding mill is found to be the main reason for the presence of residues in eggs. An animal experiment was set up to investigate the effect of carry-over at the feeding mill on the presence of residues of anticoccidials in eggs. For the compounds diclazuril, robenidine, halofuginone and nicarbazin in combination with narasin, two concentration levels were tested: the maximum allowed concentration for broilers (100%) and a concentration corresponding to 5% carry-over during feed preparation. Also dimetridazole was included in the experiment but only at one concentration level. Eggs were sampled during treatment (14 days) and for a period of 30 days after withdrawal of the anticoccidial-containing feed. Residues were determined, and deposition and depletion curves were generated. Analyses were performed by ELISA and LC-MS/MS. For all compounds, substantial residues could be found in the 5% groups, which points out the risk of carry-over at the feeding mill. The distribution of the residues between egg yolk and white was determined by analyzing both fractions.

Screening for the coccidiostats halofuginone and nicarbazin in egg and chicken muscle: development of an ELISA

Nicarbazin and halofuginone have been widely used as coccidiostats for the prevention and treatment of coccidiosis in poultry. It has been shown that accidental cross-contamination of feed can lead to residues of these compounds in eggs and/or muscle. This paper describes a direct competitive assay for detecting halofuginone and nicarbazin, developed as qualitative screening assay. In an optimized competitive ELISA, antibodies showed 50% binding inhibition at approximately 0.08 ng ml(-1) for halofuginone and 2.5 ng ml(-1) for dinitrocarbanilide (marker residue for nicarbazin). Extraction from the matrix was carried out with acetonitrile followed by a wash with hexane. The assay's detection capability (CCbeta) for halofuginone was

The preparation and properties of coprecipitated Cu-Zr-Y and Cu-Zr-La catalysts used for the steam reforming of methanol

A series of Cu-zirconia catalysts containing various additives (Y2O3, La2O3, Al2O3 and CeO2) have been prepared by coprecipitation and their activities and stabilities under operating conditions have been obtained for the steam reforming of methanol. It has been found that an yttria-promoted catalyst containing 30 mol% Cu and 20 mol% of Y2O3 is not only very active but is also very stable under reaction conditions. The yttria appears to stabilise a high copper surface area and may also have a slight promotional effect on the copper. The results obtained with this material compare very favourably with data for the best catalysts reported in the literature. (C) 2007 Published by Elsevier B.V.

Preparation and characterization of Poly(vinyl alcohol) nanocomposites made from cellulose nanofibers

A method using a combination of ball milling, acid hydrolysis, and ultrasound was developed to obtain a high yield of cellulose nanofibers from flax fibers and microcrystalline cellulose (MCC). Poly(vinyl alcohol) (PVA) nanocomposites were prepared with these additives by a solution-casting technique. The cellulose nanofibers and nanocomposite films that were produced were characterized with Fourier transform infrared spectrometry, X- ray diffraction, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. Nanofibers derived from MCC were on average approximately 8 nm in diameter and 111 nm in length. The diameter of the cellulose nanofibers produced from flax fibers was approximately 9 nm, and the length was 141 nm. A significant enhancement of the thermal and mechanical properties was achieved with a small addition of cellulose nanofibers to the polymer matrix. Interestingly, the flax nanofibers had the same reinforcing effects as MCC nanofibers in the matrix. Dynamic mechanical analysis results indicated that the use of cellulose nanofibers (acid hydrolysis) induced a mechanical percolation phenomenon leading to outstanding and unusual mechanical properties through the formation of a rigid filler network in the PVA matrix. X-ray diffraction showed that there was no significant change in the crystallinity of the PVA matrix with the incorporation of cellulose nanofibers. © 2009 Wiley Periodicals, Inc.

Performance of calcium deficient hydroxyapatite-polyglycolic acid composites: An in vitro study

The strategic incorporation of bioresorbable polymeric additives to calcium-deficient hydroxyapatite cement may provide short-term structural reinforcement and modify the modulus to closer match bone. The longer-term resorption properties may also be improved, creating pathways for bone in-growth. The aim of this study was to investigate the resorption process of a calcium phosphate cement system containing either in polyglycolic acid tri-methylene carbonate particles or polyglycolic acid fibres. This was achieved by in vitro aging in physiological conditions (phosphate buffered solution at 37°C) over 12 weeks. The unreinforced CPC exhibited an increase in compressive strength at 12 weeks, however catastrophic failure was observed above a critical loading. The fracture behaviour of cement was improved by the incorporation of PGA fibres; the cement retained its cohesive structure after critical loading. Gravimetric analysis and scanning electron microscopy showed a large proportion of the fibres had resorbed after 12 weeks allowing for the increased cement porosity, which could facilitate cell infiltration and faster integration of natural bone. Incorporating the particulate additives in the cement did not provide any mechanism for mechanical property augmentation or did not demonstrate any appreciable level of resorption after 12 weeks.

Development of ELISAs for detecting domoic acid, okadaic acid, and saxitoxin and their applicability for the detection of marine toxins in samples collected in Belgium

Okadaic acid, a diarrhetic shellfish poison, domoic acid, an amnesic shellfish poison, and saxitoxin, a paralytic shellfish poison, are three of the best-known marine biotoxins. The mouse bioassay is the method most widely used to detect many of these toxins in shellfish samples, but animal welfare concerns have prompted researchers to seek alternative methods of detection. In this study, three direct competitive enzyme-linked immunosorbent assays (ELISAs), each based on antibodies raised in rabbits against a conjugate of the analyte of interest, were developed for marine biotoxin detection in mussel, oyster, and scallop. One assay was for okadaic acid, one for saxitoxin, and one for domoic acid usually detected and quantified by high-performance liquid chromatography-ultraviolet light (HPLC-UV). All three compounds and a number of related toxins were extracted quickly and simply from the shellfish matrices with a 9 : 1 mixture of ethanol and water before analysis. The detection capabilities (CC values) of the developed ELISAs were 150 mu g kg-1 for okadaic acid, 50 mu g kg-1 for domoic acid, and 5 mu g kg-1 or less for saxitoxin. The assays proved satisfactory when used over a 4-month period for the analysis of 110 real samples collected in Belgium.

Dual functional ionic liquids as plasticisers and antimicrobial agents for medical polymers

Contamination of medical devices with bacteria such as Meticillin resistant Staphylococcus aureus (MRSA) is of great clinical concern. Poly(vinyl chloride) is widely used in the production of medical devices, such as catheters. The flexibility of catheter tubing is derived from the addition of plasticisers. Here, we report the design of two dual functional ionic liquids, 1-ethylpyridinium docusate and tributyl(2-hydroxyethyl)phosphonium docusate, which uniquely provide a plasticising effect, and exhibit antimicrobial and antibiofilm-forming activity to a range of antibiotic resistant bacteria. The plasticisation of poly(vinyl chloride) was tailored as a function of ionic liquid concentration. The effective antimicrobial behaviour of both ionic liquids originates from the chemical structure of the anion or cation and is not limited to the length of the alkyl chain on the anion/cation. The design approach adopted will be useful in developing ionic liquids as multi-functional additives for polymers.

Paralytic shellfish poisoning (PSP) toxin binders for optical biosensor technology: problems and possibilities for the future: a review

This review examines the developments in optical biosensor technology, which uses the phenomenon of surface plasmon resonance, for the detection of paralytic shellfish poisoning (PSP) toxins. Optical biosensor technology measures the competitive biomolecular interaction of a specific biological recognition element or binder with a target toxin immobilised onto a sensor chip surface against toxin in a sample. Different binders such as receptors and antibodies previously employed in functional and immunological assays have been assessed. Highlighted are the difficulties in detecting this range of low molecular weight toxins, with analogues differing at four chemical substitution sites, using a single binder. The complications that arise with the toxicity factors of each toxin relative to the parent compound, saxitoxin, for the measurement of total toxicity relative to the mouse bioassay are also considered. For antibodies, the cross-reactivity profile does not always correlate to toxic potency, but rather to the toxin structure to which it was produced. Restrictions and availability of the toxins makes alternative chemical strategies for the synthesis of protein conjugate derivatives for antibody production a difficult task. However, when two antibodies with different cross-reactivity profiles are employed, with a toxin chip surface generic to both antibodies, it was demonstrated that the cross-reactivity profile of each could be combined into a single-assay format. Difficulties with receptors for optical biosensor analysis of low molecular weight compounds are discussed, as are the potential of alternative non-antibody-based binders for future assay development in this area.

Survey of the anticoccidial feed additive nicarbazin (as dinitrocarbanilide residues) in poultry and eggs

A survey was carried out on the occurrence of dinitrocarbanilide (DNC), the marker residue for nicarbazin, in poultry produced in Ireland during 2002-2004. Liver (n = 736) and breast muscle samples (n = 342) were tested. DNC residues were found in 40 and 26% of liver and breast muscle samples at levels greater than 12.5 and 5 mu g kg(-1), respectively. DNC residues were found at >200 mu g kg(-1) in 12 and 0% of liver and muscle samples, respectively. Samples of breast muscle (n = 217) imported from 11 countries were also tested for DNC residues. A lower incidence of DNC residues (6%) was found in imported breast muscle. Egg samples (n = 546) were tested and DNC residues were found in nine samples, with levels ranging between 14 and 122 mu g kg(-1). Analysis of poultry, carried out as part of official food inspection in the period 2004-2006, indicated a reduction in the number of broiler liver samples containing DNC at >200 mu g kg(-1), to approximately 7%. Low levels of DNC residues continue to be found in