Determination of butyltin compounds in surface sediments from the São Paulo State coast (Brazil) by gas chromatography-pulsed flame photometric detection

Occurrence and the effects of butyltin compounds (BTs) have been studied for some years, mainly in countries of the Northern Hemisphere. Due to widespread use of tributyltin compounds (TBTs) and considering their deleterious effects, it is necessary to conduct studies on its occurrence, especially in the marine environment because of its excessive use in coatings of ship hulls to prevent fouling. Moreover, it was important to extend the evaluation to areas where there is no current information about their occurrence. The present work reports the occurrence of BTs in marine sediments of São Paulo state, Brazil. Commercial and leisure harbor sampling sites were selected because these areas are potentially exposed to BTs from antifouling paints used on ship hulls. Analytical conditions for organotin analysis in marine sediments were optimized for GC with pulsed flame photometric detection. Detection limits ranged from 8.4 to 66.3 ng g(-1) using a 610-nm filter, and the linearity range was 20-500 ng g(-1). Concentration levels of BTs were highest in Santos harbor (360 ng g(-1) TBT in average) and Guaruja marina (670 ng g(-1) TBT in average), which seems to be related to intensive boat traffic. Lower levels of BTs were observed in Cananeia, where only fishing boats are present (50 ng g(-1) TBT in average). (C) 2002 Elsevier B.V. B.V. All rights reserved.

Alpha1-syntrophin mutations identified in sudden infant death syndrome cause an increase in late cardiac sodium current.

BACKGROUND Sudden infant death syndrome (SIDS) is a leading cause of death during the first 6 months after birth. About 5% to 10% of SIDS may stem from cardiac channelopathies such as long-QT syndrome. We recently implicated mutations in alpha1-syntrophin (SNTA1) as a novel cause of long-QT syndrome, whereby mutant SNTA1 released inhibition of associated neuronal nitric oxide synthase by the plasma membrane Ca-ATPase PMCA4b, causing increased peak and late sodium current (I(Na)) via S-nitrosylation of the cardiac sodium channel. This study determined the prevalence and functional properties of SIDS-associated SNTA1 mutations. METHODS AND RESULTS Using polymerase chain reaction, denaturing high-performance liquid chromatography, and DNA sequencing of SNTA1's open reading frame, 6 rare (absent in 800 reference alleles) missense mutations (G54R, P56S, T262P, S287R, T372M, and G460S) were identified in 8 (approximately 3%) of 292 SIDS cases. These mutations were engineered using polymerase chain reaction-based overlap extension and were coexpressed heterologously with SCN5A, neuronal nitric oxide synthase, and PMCA4b in HEK293 cells. I(Na) was recorded using the whole-cell method. A significant 1.4- to 1.5-fold increase in peak I(Na) and 2.3- to 2.7-fold increase in late I(Na) compared with controls was evident for S287R-, T372M-, and G460S-SNTA1 and was reversed by a neuronal nitric oxide synthase inhibitor. These 3 mutations also caused a significant depolarizing shift in channel inactivation, thereby increasing the overlap of the activation and inactivation curves to increase window current. CONCLUSIONS Abnormal biophysical phenotypes implicate mutations in SNTA1 as a novel pathogenic mechanism for the subset of channelopathic SIDS. Functional studies are essential to distinguish pathogenic perturbations in channel interacting proteins such as alpha1-syntrophin from similarly rare but innocuous ones.

The nitrogen costs of photosynthesis in a diatom under current and future pCO2

With each cellular generation, oxygenic photoautotrophs must accumulate abundant protein complexes that mediate light capture, photosynthetic electron transport and carbon fixation. In addition to this net synthesis, oxygenic photoautotrophs must counter the light-dependent photoinactivation of Photosystem II (PSII), using metabolically expensive proteolysis, disassembly, resynthesis and re-assembly of protein subunits. We used growth rates, elemental analyses and protein quantitations to estimate the nitrogen (N) metabolism costs to both accumulate the photosynthetic system and to maintain PSII function in the diatom Thalassiosira pseudonana, growing at two pCO2 levels across a range of light levels. The photosynthetic system contains c. 15-25% of total cellular N. Under low growth light, N (re)cycling through PSII repair is only c. 1% of the cellular N assimilation rate. As growth light increases to inhibitory levels, N metabolite cycling through PSII repair increases to c. 14% of the cellular N assimilation rate. Cells growing under the assumed future 750 ppmv pCO2 show higher growth rates under optimal light, coinciding with a lowered N metabolic cost to maintain photosynthesis, but then suffer greater photoinhibition of growth under excess light, coincident with rising costs to maintain photosynthesis. We predict this quantitative trait response to light will vary across taxa.

Narratives and counter-narratives on "marriage of convenience" : conjugality and (il)legality in portuguese migration policies and in couples’ experiences

Tese de doutoramento, Sociologia (Sociologia da Família, Juventude e das Relações do Género), Universidade de Lisboa, Instituto de Ciências Sociais, 2016

The EU Counter-Terrorism Policy Responses to the Attacks in Paris: Towards an EU Security and Liberty Agenda. CEPS Liberty and Security in Europe No. 81/February 2015

This paper examines the main EU-level initiatives that have been put forward in the weeks following the attacks in Paris in January 2015, which will be discussed in the informal European Council meeting of 12 February 2015. It argues that a majority of these proposals predated the Paris shootings and had until that point proved contentious as regards their efficacy, legitimacy and lawfulness. The paper finds that EU counterterrorism responses raise two fundamental challenges: A first challenge is posed to the freedom of movement, Schengen and EU citizenship. Priority is being given to the expanded use of large-scale surveillance and systematic monitoring of all travellers including EU citizens, which stands in contravention of Schengen and the free movement principle. A second challenge concerns EU democratic rule of law. Current pressures calling for the adoption of measures such as the EU Passenger Name Record challenge the scrutiny roles held by the European Parliament and the Court of Justice of the EU on counterterrorism measures in a post-Lisbon Treaty setting. The paper proposes that the EU adopts a new European Agenda on Security and Liberty based on an EU security (criminal justice-led) cooperation model that is firmly anchored in current EU legal principles and rule of law standards. This model would call for ‘less is more’ concerning the use, processing and retention of data by police and intelligence communities. Instead, it would pursue better and more accurate use of data meeting the quality standards of evidence in criminal judicial proceedings.

The EU and its Counter-Terrorism Policies after the Paris Attacks. Liberty and Security in Europe No. 84, 27 November 2015

This paper examines the EU’s counter-terrorism policies responding to the Paris attacks of 13 November 2015. It argues that these events call for a re-think of the current information-sharing and preventive-justice model guiding the EU’s counter-terrorism tools, along with security agencies such as Europol and Eurojust. Priority should be given to independently evaluating ‘what has worked’ and ‘what has not’ when it comes to police and criminal justice cooperation in the Union. Current EU counter-terrorism policies face two challenges: one is related to their efficiency and other concerns their legality. ‘More data’ without the necessary human resources, more effective cross-border operational cooperation and more trust between the law enforcement authorities of EU member states is not an efficient policy response. Large-scale surveillance and preventive justice techniques are also incompatible with the legal and judicial standards developed by the Court of Justice of the EU. The EU can bring further added value first, by boosting traditional policing and criminal justice cooperation to fight terrorism; second, by re-directing EU agencies’ competences towards more coordination and support in cross-border operational cooperation and joint investigations, subject to greater accountability checks (Europol and Eurojust +); and third, by improving the use of policy measures following a criminal justice-led cooperation model focused on improving cross-border joint investigations and the use of information that meets the quality standards of ‘evidence’ in criminal judicial proceedings. Any EU and national counter-terrorism policies must not undermine democratic rule of law, fundamental rights or the EU’s founding constitutional principles, such as the free movement of persons and the Schengen system. Otherwise, these policies will defeat their purpose by generating more insecurity, instability, mistrust and legal uncertainty for all.

Therapeutic drug monitoring of cefepime with micellar electrokinetic capillary chromatography: Assay improvement, quality assurance, and impact on patient drug levels

The improvement and performance of a micellar electrokinetic capillary chromatography assay for cefepime in human serum and plasma with a 50 μm id fused-silica capillary elongated from 40 to 60 cm is reported. Sample preparation with dodecylsulfate protein precipitation at pH 4.5, the pH 9.1 separation medium and the applied voltage were as reported previously[16]. The change resulted in a significant lower current, higher resolution and increased detection time intervals. The performance of the assay with multi-level internal calibration was assessed with calibration and control samples. Quality assurance data of a two year period assessed under the new conditions demonstrated the robustness of the assay. In serum samples of patients who received both cefepime and sulfamethoxazole, cefepime could not be detected due to the inseparability of the two compounds. The presence of an interference can be recognized by an increased peak width (width > 0.2 min), the appearance of a shoulder or an unresolved double peak. The patient data gathered during a three year period reveal that introduction of therapeutic drug monitoring led to a 50% reduction of the median drug level. The data suggest that therapeutic drug monitoring can help to minimize the risk of major adverse reactions and to increase drug safety on an individual basis. This article is protected by copyright. All rights reserved.

Organizational, DS, GS, and depot maintenance manual : radiac set, AN/PDR-60 (Eberline Instrument Corporation portable alpha counter model PAC-1SAGA).

"January 1966."

Measurement of free drug and clinical end-point by high-performance liquid chromatography-mass spectrometry: Applications and implications for pharmacokinetic and pharmacodynamic studies

Free drug measurement and pharmacodymanic markers provide the opportunity for a better understanding of drug efficacy and toxicity. High-performance liquid chromatography (HPLC)-mass spectrometry (MS) is a powerful analytical technique that could facilitate the measurement of free drug and these markers. Currently, there are very few published methods for the determination of free drug concentrations by HPLC-MS. The development of atmospheric pressure ionisation sources, together with on-line microdialysis or on-line equilibrium dialysis and column switching techniques have reduced sample run times and increased assay efficiency. The availability of such methods will aid in drug development and the clinical use of certain drugs, including anti-convulsants, anti-arrhythmics, immunosuppressants, local anaesthetics, anti-fungals and protease inhibitors. The history of free drug measurement and an overview of the current HPLC-MS applications for these drugs are discussed. Immunosuppressant drugs are used as an example for the application of HPLC-MS in the measurement of drug pharmacodynamics. Potential biomarkers of immunosuppression that could be measured by HPLC-MS include purine nucleoside/nucleotides, drug-protein complexes and phosphorylated peptides. At the proteomic level, two-dimensional gel electrophoresis combined with matrix-assisted laser desorption/ionisation time-of-flight (TOF) MS is a powerful tool for identifying proteins involved in the response to inflammatory mediators. (C) 2003 Elsevier Science B.V. All rights reserved.

Matrix effects: The Achilles heel of quantitative high-performance liquid chromatography-electrospray-tandem mass spectrometry

High-performance liquid chromatography coupled by an electrospray ion source to a tandem mass spectrometer (HPLC-EST-MS/ MS) is the current analytical method of choice for quantitation of analytes in biological matrices. With HPLC-ESI-MS/MS having the characteristics of high selectivity, sensitivity, and throughput, this technology is being increasingly used in the clinical laboratory. An important issue to be addressed in method development, validation, and routine use of HPLC-ESI-MS/MS is matrix effects. Matrix effects are the alteration of ionization efficiency by the presence of coeluting substances. These effects are unseen in the chromatograrn but have deleterious impact on methods accuracy and sensitivity. The two common ways to assess matrix effects are either by the postextraction addition method or the postcolumn infusion method. To remove or minimize matrix effects, modification to the sample extraction methodology and improved chromatographic separation must be performed. These two parameters are linked together and form the basis of developing a successful and robust quantitative HPLC-EST-MS/MS method. Due to the heterogenous nature of the population being studied, the variability of a method must be assessed in samples taken from a variety of subjects. In this paper, the major aspects of matrix effects are discussed with an approach to address matrix effects during method validation proposed. (c) 2004 The Canadian Society of Clinical Chemists. All rights reserved.

Mechanism and kinetics of dithiobenzoate-mediated RAFT polymerization. I. The current situation

Investigations into the kinetics and mechanism of dithiobenzoate-mediated Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerizations, which exhibit nonideal kinetic behavior, such as induction periods and rate retardation, are comprehensively reviewed. The appreciable uncertainty in the rate coefficients associated with the RAFT equilibrium is discussed and methods for obtaining RAFT-specific rate coefficients are detailed. In addition, mechanistic studies are presented, which target the elucidation of the fundamental cause of rate retarding effects. The experimental and theoretical data existing in the literature are critically evaluated and apparent discrepancies between the results of different studies into the kinetics of RAFT polymerizations are discussed. Finally, recommendations for further work are given. (c) 2006 Wiley Periodicals, Inc.

The measurements of neutron and gamma dose rates in mixed radiation fields, using a liquid scintillation counter

Measurements of neutron and gamma dose rates in mixed radiation fields, and gamma dose rates from calibrated gamma sources, were performed using a liquid scintillation counter NE213 with a pulse shape discrimination technique based on the charge comparison method. A computer program was used to analyse the experimental data. The radiation field was obtained from a 241Am-9Be source. There was general agreement between measured and calculated neutron and gamma dose rates in the mixed radiation field, but some disagreement in the measurements of gamma dose rates for gamma sources, due to the dark current of the photomultiplier and the effect of the perturbation of the radiation field by the detector. An optical fibre bundle was used to couple an NE213 scintillator to a photomultiplier, in an attempt to minimise these effects. This produced an improvement in the results for gamma sources. However, the optically coupled detector system could not be used for neutron and gamma dose rate measurements in mixed radiation fields. The pulse shape discrimination system became ineffective as a consequence of the slower time response of the detector system.

Beyond the Pay: Current Illicit Activities of the Armed Forces in Central America

The growth of criminal gangs and organized crime groups has created unprecedented challenges in Central America. Homicide rates are among the highest in the world, countries spend on average close to 10 percent of GDP to respond to the challenges of public insecurity, and the security forces are frequently overwhelmed and at times coopted by the criminal groups they are increasingly tasked to counter. With some 90 percent of the 700 metric tons of cocaine trafficked from South America to the United States passing through Central America, the lure of aiding illegal traffickers through provision of arms, intelligence, or simply withholding or delaying the use of force is enormous. These conditions raise the question: to what extent are militaries in Central America compromised by illicit ties to criminal groups? The study focuses on three cases: Nicaragua, El Salvador, and Honduras. It finds that: Although illicit ties between the military and criminal groups have grown in the last decade, militaries in these countries are not yet “lost’ to criminal groups. Supplying criminal groups with light arms from military stocks is typical and on the rise, but still not common. In general the less exposed services, the navies and air forces, are the most reliable and effective ones in their roles in interdiction. Of the three countries in the study, the Honduran military is the most worrying because it is embedded in a context where civilian corruption is extremely common, state institutions are notoriously weak, and the political system remains polarized and lacks the popular legitimacy and political will needed to make necessary reforms. Overall, the armed forces in the three countries remain less compromised than civilian peers, particularly the police. However, in the worsening crime and insecurity context, there is a limited window of opportunity in which to introduce measures targeted toward the military, and such efforts can only succeed if opportunities for corruption in other sectors of the state, in particular in law enforcement and the justice system, are also addressed. Measures targeted toward the military should include: Enhanced material benefits and professional education opportunities that open doors for soldiers in promising legitimate careers once they leave military service. A clear system of rewards and punishments specifically designed to deter collusion with criminal groups. More effective securing of military arsenals. Skills and external oversight leveraged through combined operations, to build cooperation among those sectors of the military that have successful and clean records in countering criminal groups, and to expose weaker forces to effective best practices.