Low pressure carbon dioxide solubility in pure electrolyte solvents for lithium-ion batteries as a function of temperature. Measurement and prediction

Experimental values for the carbon dioxide solubility in eight pure electrolyte solvents for lithium ion batteries – such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ?-butyrolactone (?BL), ethyl acetate (EA) and methyl propionate (MP) – are reported as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility data, the Henry’s law constant of the carbon dioxide in these solvents was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOthermX software and those calculated by the Peng–Robinson equation of state implemented into Aspen plus. From this work, it appears that the CO2 solubility is higher in linear carbonates (such as DMC, EMC, DEC) than in cyclic ones (EC, PC, ?BL). Furthermore, the highest CO2 solubility was obtained in MP and EA solvents, which are comparable to the solubility values reported in classical ionicliquids. The precision and accuracy of the experimental values, considered as the per cent of the relative average absolute deviations of the Henry’s law constants from appropriate smoothing equations and from literature values, are close to (1% and 15%), respectively. From the variation of the Henry’s law constants with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs free energy, the enthalpy, and the entropy are calculated, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state.

Genome-wide Association Study Implicates HLA-C*01:02 as a Risk Factor at the Major Histocompatibility Complex Locus in Schizophrenia

BACKGROUND: We performed a genome-wide association study (GWAS) to identify common risk variants for schizophrenia. METHODS: The discovery scan included 1606 patients and 1794 controls from Ireland, using 6,212,339 directly genotyped or imputed single nucleotide polymorphisms (SNPs). A subset of this sample (270 cases and 860 controls) was subsequently included in the Psychiatric GWAS Consortium-schizophrenia GWAS meta-analysis. RESULTS: One hundred eight SNPs were taken forward for replication in an independent sample of 13,195 cases and 31,021 control subjects. The most significant associations in discovery, corrected for genomic inflation, were (rs204999, p combined = 1.34 × 10(-9) and in combined samples (rs2523722 p combined = 2.88 × 10(-16)) mapped to the major histocompatibility complex (MHC) region. We imputed classical human leukocyte antigen (HLA) alleles at the locus; the most significant finding was with HLA-C*01:02. This association was distinct from the top SNP signal. The HLA alleles DRB1*03:01 and B*08:01 were protective, replicating a previous study. CONCLUSIONS: This study provides further support for involvement of MHC class I molecules in schizophrenia. We found evidence of association with previously reported risk alleles at the TCF4, VRK2, and ZNF804A loci.

Monoclonal antibody-based ELISA for the quantification of nitrofuran metabolite 3-amino-2-oxazolidinone in tissues using a simplified sample preparation

A sensitive and specific monoclonal ELISA for the determination of tissue bound furazolidone metabolite 3-amino-2-oxazolidinone (AOZ) is described. The procedure enables the detection of AOZ in matrix supernatant after homogenisation, protease treatment, acid hydrolysis and derivatisation of AOZ released from the tissue by o-nitrobenzaldehyde. The formed p-nitrophenyl 3-amino-2-oxazolidinone (NPAOZ) is determined by ELISA calibrated with matrix-matched standards in the concentration range of 0.05-5.0 mu g l(-1). The assay was validated according to criteria set down by Commission Decision 2002/657/EC for the performance and validation of analytical methods for chemical residues. Detection capability, set on the basis of acceptance of no false negative results, was 0.4 mu g kg(-1) for shrimp, poultry, beef and pork muscle. This sensitivity approaches the established confirmatory LC-MS/MS able to quantify tissue-bound AOZ at levels as low as 0.3 mu g kg(-1). An excellent correlation of results obtained by ELISA and LC/MS-MS within the concentration range 0-32.1 mu g kg(-1) was found in the naturally contaminated shrimp samples (r = 0.999, n = 8). A similar con-elation was found for the incurred poultry samples within the concentration range of 0-10.5 mu g kg(-1) (r = 0.99, n = 8). (c) 2005 Elsevier B.V All rights reserved.

Preparing the ground for marine spatial planning in Ireland

Marine spatial planning (MSP) is advocated as a means of managing human uses of the sea in a manner that is consistent with the maintenance of the ecological goods and services of the marine environment. The adoption of a system of MSP is seen as urgent in the face of ever-increasing demands on marine resources. This is particularly so in Ireland with its extensive seas, belatedly being recognised as a significant development resource. MSP is promoted by the European Commission (EC) in a recent Green Paper to which Member States of the Union, including Ireland, generally have responded positively. Arising from this consultative process, the EC has published the 'Blue Book' that commits support for MSP. It has also issued guidelines for an integrated approach to maritime policy. The recently adopted EU Marine Strategy Framework Directive strengthens the case for implementing MSP as it requires each Member State to develop a strategy for its marine resources. There is evidence that a diverse range of stakeholders at national and local levels in Ireland are positively disposed toward MSP but no practical manifestation of the concept is in place, though some preparatory work is underway to facilitate its likely implementation into the future. © 2010 WIT Press.

The indirect effects of biofuels and what to do about them:The case of grass biomethane and its impact on livestock

Grass biomethane surpasses the 60% greenhouse gas (GHG) savings relative to the fossil fuel replaced required by EU Directive 2009/28/EC. However, there are growing concerns that when the indirect effects of biofuels are taken into account, GHG savings may become negative. There has been no research to date into the indirect effects of grass biomethane; this paper aims to fill that knowledge gap. A causal-descriptive assessment is carried out and identifies the likely indirect effect of a grass biomethane industry in Ireland as a reduction in beef exports to the UK. Three main scenarios are then analyzed: an increase in indigenous UK beef production, an increase in beef imported to the UK from other countries (EU, New Zealand and Brazil), and a decrease in beef consumption leading to increased poultry consumption. The GHG emissions from each of these scenarios are determined and the resulting savings relative to fossil diesel vary between -636% and 102%. The significance of the findings is then discussed. It is the view of the authors that, while consideration of indirect effects is important, an Irish grass biomethane industry cannot be held accountable for the associated emissions. A global GHG accounting system is therefore proposed; however, the difficulty of implementing such a system is acknowledged, as is its probable ineffectualness. Such a system would not treat the source of the problem - rising consumption. The authors conclude that the most effective method of combating the indirect effects of biofuels is a reduction in general consumption. © 2011 Society of Chemical Industry and John Wiley & Sons, Ltd.

Can we meet targets for biofuels and renewable energy in transport given the constraints imposed by policy in agriculture and energy?

The deployment of biofuels is significantly affected by policy in energy and agriculture. In the energy arena, concerns regarding the sustainability of biofuel systems and their impact on food prices led to a set of sustainability criteria in EU Directive 2009/28/EC on Renewable Energy. In addition, the 10% biofuels target by 2020 was replaced with a 10% renewable energy in transport target. This allows the share of renewable electricity used by electric vehicles to contribute to the mix in achieving the 2020 target. Furthermore, only biofuel systems that effect a 60% reduction in greenhouse gas emissions by 2020 compared with the fuel they replace are allowed to contribute to meeting the target. In the agricultural arena, cross-compliance (which is part of EU Common Agricultural Policy) dictates the allowable ratio of grassland to total agricultural land, and has a significant impact on which biofuels may be supported. This paper outlines the impact of these policy areas and their implications for the production and use of biofuels in terms of the 2020 target for 10% renewable transport energy, focusing on Ireland. The policies effectively impose constraints on many conventional energy crop biofuels and reinforce the merits of using biomethane, a gaseous biofuel. The analysis shows that Ireland can potentially satisfy 15% of renewable energy in transport by 2020 (allowing for double credit for biofuels from residues and ligno-cellulosic materials, as per Directive 2009/28/EC) through the use of indigenous biofuels: grass biomethane, waste and residue derived biofuels, electric vehicles and rapeseed biodiesel. © 2010 Elsevier Ltd. All rights reserved.

The Anti-Migratory Effects of FKBPL and Its Peptide Derivative, AD-01: Regulation of CD44 and the Cytoskeletal Pathway

FK506 binding protein-like (FKBPL) and its peptide derivatives exert potent anti-angiogenic activity and and control tumour growth in xenograft models, when administered exogenously. However, the role of endogenous FKBPL in angiogenesis is not well characterised. Here we investigated the molecular effects of the endogenous protein and its peptide derivative, AD-01, leading to their anti-migratory activity. Inhibition of secreted FKBPL using a blocking antibody or siRNA-mediated knockdown of FKBPL accelerated the migration of human microvascular endothelial cells (HMEC-1). Furthermore, MDA-MB-231 tumour cells stably overexpressing FKBPL inhibited tumour vascular development suggesting that FKBPL secreted from tumour cells could inhibit angiogenesis. Whilst FKBPL and AD-01 target CD44, the nature of this interaction is not known and here we have further interrogated this aspect. We have demonstrated that FKBPL and AD-01 bind to the CD44 receptor and inhibit tumour cell migration in a CD44 dependant manner; CD44 knockdown abrogated AD-01 binding as well as its anti-migratory activity. Interestingly, FKBPL overexpression and knockdown or treatment with AD-01, regulated CD44 expression, suggesting a co-regulatory pathway for these two proteins. Downstream of CD44, alterations in the actin cytoskeleton, indicated by intense cortical actin staining and a lack of cell spreading and communication were observed following treatment with AD-01, explaining the anti-migratory phenotype. Concomitantly, AD-01 inhibited Rac-1 activity, up-regulated RhoA and the actin binding proteins, profilin and vinculin. Thus the anti-angiogenic protein, FKBPL, and AD-01, offer a promising and alternative approach for targeting both CD44 positive tumours and vasculature networks.

Targeting treatment resistant breast cancer stem cells with FKBPL and its peptide derivative, AD-01, via the CD44 pathway

PURPOSE: FKBPL and its peptide derivative, AD-01, have already demonstrated tumour growth inhibition and CD44 dependent anti-angiogenic activity. Here we explore the ability of AD-01 to target CD44 positive breast cancer stem cells (BCSCs). EXPERIMENTAL DESIGN: Mammosphere assays and flow cytometry were utilized to analyse the effect of FKBPL overexpression/knockdown and AD-01 treatment ± other anti-cancer agents on BCSCs using breast cancer cell lines (MCF-7/MDA-231/ZR-75), primary patient samples and xenografts. Delays in tumour initiation were evaluated in vivo. The anti-stem cell mechanisms were determined using clonogenic assays, qPCR and immunofluorescence. RESULTS: AD-01 treatment was highly effective at inhibiting the BCSC population by reducing mammosphere forming efficiency (MFE) and ESA+/CD44+/CD24- or ALDH+ cell subpopulations in vitro and tumour initiation in vivo. The ability of AD-01 to inhibit the self-renewal capacity of BCSCs was confirmed; mammospheres were completely eradicated by the third generation. The mechanism appears to be due to AD-01-mediated BCSC differentiation demonstrated by a significant decrease in the number of holoclones and an associated increase in meroclones/paraclones; the stem cell markers, Nanog, Oct4 and Sox2, were also significantly reduced. Furthermore, we demonstrated additive inhibitory effects when AD-01 was combined with the Notch inhibitor, DAPT. AD-01 was also able to abrogate a chemo- and radiotherapy induced enrichment in BCSCs. Finally, FKBPL knockdown led to an increase in Nanog/Oct4/Sox2 and an increase in BCSCs, highlighting a role for endogenous FKBPL in stem cell signalling. CONCLUSIONS: AD-01 has dual anti-angiogenic and anti-BCSC activity which will be advantageous as this agent enters clinical trial.

Assessing suspended sediment dynamics in relation to ecological thresholds and sampling strategies in two Irish headwater catchments

Prediction of the impact of suspended sediment on aquatic ecosystems requires adequate knowledge of sediment dynamics in surface waters. Often, studies reporting the response of aquatic biota to suspended sediment are concerned with concentrations, while catchment erosion studies often report sediment delivery as annual loads and yields, making the comparison to documented ecological impacts difficult. Similarly, the European Union Freshwater Fish Directive (FFD) (78/659/EC) stipulates a guideline value of 25mgl which should not be exceeded, with the exception of floods and droughts. In this respect, the significance of suspended sediment in two Irish rivers was assessed using turbidity sensors calibrated for suspended sediment. Sediment yields of 0.07 tonnes (t) hayear and 0.44thayear and annual FFD exceedance frequency of 8.3% and 17.8% were estimated for the two catchments. Contrasts in the frequency of exceedance events between both catchments was observed, yet duration was typically short (

Single-laboratory validation of a multiplex flow cytometric immunoassay for the simultaneous detection of coccidiostats in eggs and feed

Coccidiostats are authorized in the European Union (EU) to be used as poultry feed additives. Maximum (residue) levels (M(R)Ls) have been set within the EU for consumer and animal protection against unintended carry-over, and monitoring is compulsory. This paper describes the single-laboratory validation of a previously developed multiplex flow cytometric immunoassay (FCIA) as screening method for coccidiostats in eggs and feed and provides and compares different approaches for the calculation of the cut-off levels which are not described in detail within Commission Decision 2002/657/EC. Comparable results were obtained between the statistical (reference) approach and the rapid approaches. With the most rapid approach, the cut-off levels for narasin/salinomycin, lasalocid, diclazuril, nicarbazin (DNC) and monensin in egg, calculated as percentages of inhibition (%B/B0), were 60, 32, 76, 80 and 84, respectively. In feed, the cut-off levels for narasin/salinomycin, lasalocid, nicarbazin (DNC) and monensin were 70, 64, 72 and 78, respectively, and could not be determined for diclazuril. For all analytes, except for diclazuril in feed, the rate of false positives (false non-compliant) in blank samples was lower than 1 %, and the rate of false negatives (false compliant) at the M(R)Ls was below 5 %. Additionally, very good correlations (r ranging from 0.994 to 0.9994) were observed between two different analysers, a sophisticated flow cytometer (FlexMAP 3D(®)) and a more cost-efficient and transportable planar imaging detector (MAGPIX(®)), hence demonstrating adequate transferability.

Comparison of sample preparation methods, validation of an UPLC-MS/MS procedure for the quantification of tetrodotoxin present in marine gastropods and analysis of pufferfish

Tetrodotoxin (TTX) is one of the most potent marine neurotoxins reported. The global distribution of this toxin is spreading with the European Atlantic coastline now being affected. Climate change and increasing pollution have been suggested as underlying causes for this. In the present study, two different sample preparation techniques were used to extract TTX from Trumpet shells and pufferfish samples. Both extraction procedures (accelerated solvent extraction (ASE) and a simple solvent extraction) were shown to provide good recoveries (80-92%). A UPLC-MS/MS method was developed for the analysis of TTX and validated following the guidelines contained in the Commission Decision 2002/657/EC for chemical contaminant analysis. The performance of this procedure was demonstrated to be fit for purpose. This study is the first report on the use of ASE as a mean for TTX extraction, the use of UPLC-MS/MS for TTX analysis, and the validation of this method for TTX in gastropods.

Autonomous collective agreements as a regulatory device in European labour law:How to read Article 139 EC

This article discusses whether European social partners can derive the competence to autonomously devise European collective labour agreements from Article 139 EC (equals Article III-212 Constitution of Europe). Placing the question in the context of discussions of EU governance and private lawmaking in general, the author starts with a comparative overview of legal conceptions for collective labour agreements in Europe, focusing on three Member States' orders where their effects are not or only partly regulated by state legislation. Based on this comparison, she analyses Article 139(2) and offers a new interpretation of its provisions concerning autonomous implementation of European social partner agreements. She concludes that European social partners do have the competence to agree on a basic agreement stating the rules for European collective bargaining autonomously.

Elements of A New Framework for the principle of Equal Treatment of persons in EC Law

In June and November 2000, the European Parliament and the Council adopted two Directives referring to ‘the principle of equal treatment irrespective of’ in their title, one relating to racial and ethnic origin, the other to disability, age, religion and belief or sexual orientation. A thorough reform of Directive 76/207/EEC on the principle of equal treatment for women and men in employment matters is pending between the European Parliament's second reading and adoption while this is written. Community secondary legislation on equal treatment of persons has thus expanded in scope and number of reasons which must not serve as starting points for differentiation. Does this signify progress in legal protection against personal discrimination? While not providing a ready answer, this article proposes an analytical framework to answer this question, concentrating on conceptions of equality in general and in particular on the problems multi-dimensional discrimination might pose for the law.