Electrochemical sensor for simultaneous determination of herbicide MCPA and its metabolite 4-chloro-2-methylphenol. Application to photodegradation environmental monitoring

The development and application of a polyaniline/carbon nanotube (CNT) cyclodextrin matrix (PANI-β-CD/MWCNT)-based electrochemical sensor for the quantitative determination of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) and its main transformation product 4-chloro-2-methylphenol in natural waters are described. A simple cyclic voltammetry-based electrochemical methodology, in phosphate buffer solution at pH 6.0, was used to develop a method to determine both MCPA and 4-chloro-2-methylphenol, without any previous extraction or derivatization steps. A linear concentration range (10 to 50 μmol L−1) and detection limits of 1.1 and 1.9 μmol L−1, respectively, were achieved using optimized cyclic voltammetric parameters. The proposed method was successfully applied to the determination of MCPA and 4-chloro-2-methylphenol in natural water samples with satisfactory recoveries (94 to 107 %) and in good agreement with the results obtained by an established high-performance liquid chromatography technique, no significant differences being found between the methods. Interferences from ionic species and other herbicides used for broad-leaf weed control were shown to be small. The newly developed methodology was also successfully applied to MCPA photodegradation environmental studies.

Yeast resistance and its reversion

Actualmente, a resistência a drogas é um dos grandes problemas na terapia de diferentes patologias e também na biotecnologia e agricultura. O objectivo do presente estudo foi elucidar a resistência a drogas em leveduras patogénicas ou alimentares, que mais frequentemente são encontradas. Assim, diferentes antifungicos clínicos e novos compostos recentemente sintetizados foram testados por um método para avaliar a resistência e sua reversão que foi previamente desenvolvido. Foi testado um painel de diferentes drogas para reverter a resistência. Mostramos que alguns destes moduladores foram capazes de reverter eficazmente a resistência.

QuEChERS: a new sample preparation approach for the determination of ibuprofen and its metabolites in soils

Ibuprofen is one of the most used active pharmaceutical ingredients worldwide. A new method for the analysis of ibuprofen and its metabolites, hydroxyibuprofen and carboxyibuprofen, in soils is presented. The extraction of these compounds from the soil matrices was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The method involves a single extraction of the investigated compounds with purified water (acidified at pH 2.5 with hydrochloric acid), and a slow and continuous addition of the QuEChERS content, followed by the addition of acidified acetonitrile (1% acetic acid), prior to the determination by liquid chromatography coupled with fluorescence detection (LC–FLD). Validation studies were carried out using soil samples with a range of organic carbon contents. Recoveries of the fortified samples ranged from 79.5% to 101%. Relative standard deviations for all matrix–compound combinations did not exceed 3%. The method quantification limits were ≤22.4 μg kg−1 in all cases. The developed method was applied to the analysis of sixteen real samples.

Computational analysis of quinoxalines N,N-Dioxide and ITS Derivates

A quinoxalina e seus derivativos são uma importante classe de compostos heterocíclicos, onde os elementos N, S e O substituem átomos de carbono no anel. A fórmula molecular da quinoxalina é C8H6N2, formada por dois anéis aromáticos, benzeno e pirazina. É rara em estado natural, mas a sua síntese é de fácil execução. Modificações na estrutura da quinoxalina proporcionam uma grande variedade de compostos e actividades, tais como actividades antimicrobiana, antiparasitária, antidiabética, antiproliferativa, anti-inflamatória, anticancerígena, antiglaucoma, antidepressiva apresentando antagonismo do receptor AMPA. Estes compostos também são importantes no campo industrial devido, por exemplo, ao seu poder na inibição da corrosão do metal. A química computacional, ramo natural da química teórica é um método bem desenvolvido, utilizado para representar estruturas moleculares, simulando o seu comportamento com as equações da física quântica e clássica. Existe no mercado uma grande variedade de ferramentas informaticas utilizadas na química computacional, que permitem o cálculo de energias, geometrias, frequências vibracionais, estados de transição, vias de reação, estados excitados e uma variedade de propriedades baseadas em várias funções de onda não correlacionadas e correlacionadas. Nesta medida, a sua aplicação ao estudo das quinoxalinas é importante para a determinação das suas características químicas, permitindo uma análise mais completa, em menos tempo, e com menos custos.

Should the U.S. adapt to the world? The first debate on american exceptionalism and its impact on the founding of the United States

This paper aims at putting into perspective the recent, post 9/11 debate on the United States‘ alleged exceptionalism and its impact on the definition of American foreign policy. It reminds the readers that the United States was born as a result of a similar debate, at a time when a crucial choice for its future was to be made. Indeed, the Founding Fathers discarded the revolutionary idea that America was altogether different from other (European) nations and, as such, could succeed in saving republicanism and concentrate on domestic affairs. As Gordon Wood and Harvey Mansfield have shown, the 1787 version of republicanism stood as a departure from its earlier version, and such a change was necessary to the creation of a full-fledged federation, therefore paving the way to the current powerful Federal Republic. The early failure of the exceptionalist creed did not cause its disappearance, as the contemporary form of exceptionalism demonstrates, but created conditions that made an enduring and powerful influence very difficult.

Oxidative behaviour of apomorphine and its metabolites

The metabolism of apomorphine is quite complex due to interactions with proteins and other tissue components that affect its pharmacokinetic profile. The electrochemical oxidation mechanism of apomorphine and of some synthesised apomorphine derivatives was studied. It was found to be related to the reaction of o-diphenol and tertiary amine groups and strongly dependent on pH.

Study of the voltammetric behaviour of metam and its application to an amperometric flow system

The electrochemical behaviour of the pesticide metam (MT) at a glassy carbon working electrode (GCE) and at a hanging mercury drop electrode (HMDE) was investigated. Different voltammetric techniques, including cyclic voltammetry (CV) and square wave voltammetry (SWV), were used. An anodic peak (independent of pH) at +1.46 V vs AgCl/Ag was observed in MTaqueous solution using the GCE. SWV calibration curves were plotted under optimized conditions (pH 2.5 and frequency 50 Hz), which showed a linear response for 17–29 mg L−1. Electrochemical reduction was also explored, using the HMDE. A well defined cathodic peak was recorded at −0.72 V vs AgCl/ Ag, dependent on pH. After optimizing the operating conditions (pH 10.1, frequency 150 Hz, potential deposition −0.20 V for 10 s), calibration curves was measured in the concentration range 2.5×10−1 to 1.0 mg L−1 using SWV. The electrochemical behaviour of this compound facilitated the development of a flow injection analysis (FIA) system with amperometric detection for the quantification of MT in commercial formulations and spiked water samples. An assessment of the optimal FIA conditions indicated that the best analytical results were obtained at a potential of +1.30 V, an injection volume of 207 μL and an overall flow rate of 2.4 ml min−1. Real samples were analysed via calibration curves over the concentration range 1.3×10−2 to 1.3 mg L−1. Recoveries from the real samples (spiked waters and commercial formulations) were between 97.4 and 105.5%. The precision of the proposed method was evaluated by assessing the relative standard deviation (RSD %) of ten consecutive determinations of one sample (1.0 mg L−1), and the value obtained was 1.5%.

Determination of methiocarb and Its degradation products, methiocarb sulfoxide and methiocarb sulfone, in bananas using QuEChERS extraction

The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LCPAD). Calibration curves were linear in the range of 0.5−10 mg L−1 for all compounds studied. The average recoveries, measured at 0.1 mg kg−1 wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

Slotted wiDom: schedulability analysis and its experimental validation

WiDom is a wireless prioritized medium access control protocol which offers a very large number of priority levels. Hence, it brings the potential to employ non-preemptive static-priority scheduling and schedulability analysis for a wireless channel assuming that the overhead of WiDom is modeled properly. One schedulability analysis for WiDom has already been proposed but recent research has created a new version of WiDom (we call it: Slotted WiDom) with lower overhead and for this version of WiDom no schedulability analysis exists. In this paper we propose a new schedulability analysis for slotted WiDom and extend it to work also for message streams with release jitter. We have performed experiments with an implementation of slotted WiDom on a real-world platform (MicaZ). We find that for each message stream, the maximum observed response time never exceeds the calculated response time and hence this corroborates our belief that our new scheduling theory is applicable in practice.

Microencapsulation of herbicide MCPA with native beta-cyclodextrin and its methyl and hydroxypropyl derivatives: An experimental and theoretical investigation

When a pesticide is released into the environment, most of it is lost before it reaches its target. An effective way to reduce environmental losses of pesticides is by using controlled release technology. Microencapsulation becomes a promising technique for the production of controlled release agricultural formulations. In this work, the microencapsulation of chlorophenoxy herbicide MCPA with native b-cyclodextrin and its methyl and hydroxypropyl derivatives was investigated. The phase solubility study showed that both native and b-CD derivatives increased the water solubility of the herbicide and inclusion complexes are formed in a stoichiometric ratio of 1:1. The stability constants describing the extent of formation of the complexes have been determined by phase solubility studies. 1H NMR experiments were also accomplished for the prepared solid systems and the data gathered confirm the formation of the inclusion complexes. 1H NMR data obtained for the MCPA/CDs complexes disclosed noticeable proton shift displacements for OCH2 group and H6 aromatic proton of MCPA provided clear evidence of inclusion complexation process, suggesting that the phenyl moiety of the herbicide was included in the hydrophobic cavity of CDs. Free energy molecular mechanics calculations confirm all these findings. The gathered results can be regarded as an essential step to the development of controlled release agricultural formulations containing herbicide MCPA.

Multilayer Perceptron Neural Networks Training Through Charged System Search and its Application for Non-Technical Losses Detection

The non-technical loss is not a problem with trivial solution or regional character and its minimization represents the guarantee of investments in product quality and maintenance of power systems, introduced by a competitive environment after the period of privatization in the national scene. In this paper, we show how to improve the training phase of a neural network-based classifier using a recently proposed meta-heuristic technique called Charged System Search, which is based on the interactions between electrically charged particles. The experiments were carried out in the context of non-technical loss in power distribution systems in a dataset obtained from a Brazilian electrical power company, and have demonstrated the robustness of the proposed technique against with several others natureinspired optimization techniques for training neural networks. Thus, it is possible to improve some applications on Smart Grids.

Safety climate and its relationship with furniture companies’ safety performance and workers’ risk acceptance

This study aims to analyse the relationship between safety climate and the level of risk acceptance, as well as its relationship with workplace safety performance. The sample includes 14 companies and 403 workers. The safety climate assessment was performed by the application of a Safety Climate in Wood Industries questionnaire and safety performance was assessed with a checklist. Judgements about risk acceptance were measured through questionnaires together with four other variables: trust, risk perception, benefit perception and emotion. Safety climate was found to be correlated with workgroup safety performance, and it also plays an important role in workers’ risk acceptance levels. Risk acceptance tends to be lower when safety climate scores of workgroups are high, and subsequently, their safety performance is better. These findings seem to be relevant, as they provide Occupational, Safety and Health practitioners with a better understanding of workers’ risk acceptance levels and of the differences among workgroups.

Reliable link quality estimation in low-power wireless networks and its impact on tree-routing

Radio link quality estimation is essential for protocols and mechanisms such as routing, mobility management and localization, particularly for low-power wireless networks such as wireless sensor networks. Commodity Link Quality Estimators (LQEs), e.g. PRR, RNP, ETX, four-bit and RSSI, can only provide a partial characterization of links as they ignore several link properties such as channel quality and stability. In this paper, we propose F-LQE (Fuzzy Link Quality Estimator, a holistic metric that estimates link quality on the basis of four link quality properties—packet delivery, asymmetry, stability, and channel quality—that are expressed and combined using Fuzzy Logic. We demonstrate through an extensive experimental analysis that F-LQE is more reliable than existing estimators (e.g., PRR, WMEWMA, ETX, RNP, and four-bit) as it provides a finer grain link classification. It is also more stable as it has lower coefficient of variation of link estimates. Importantly, we evaluate the impact of F-LQE on the performance of tree routing, specifically the CTP (Collection Tree Protocol). For this purpose, we adapted F-LQE to build a new routing metric for CTP, which we dubbed as F-LQE/RM. Extensive experimental results obtained with state-of-the-art widely used test-beds show that F-LQE/RM improves significantly CTP routing performance over four-bit (the default LQE of CTP) and ETX (another popular LQE). F-LQE/RM improves the end-to-end packet delivery by up to 16%, reduces the number of packet retransmissions by up to 32%, reduces the Hop count by up to 4%, and improves the topology stability by up to 47%.

New molecularly-imprinted polymer for carnitine and its application as ionophore in potentiometric selective membranes

Carnitine (CRT) is a biological metabolite found in urine that contributes in assessingseveral disease conditions, including cancer. Novel quick screening procedures for CRT are therefore fundamental. This work proposes a novel potentiometric device where molecularly imprinted polymers (MIPs) were used as ionophores. The host-tailored sites were imprinted on a polymeric network assembled by radical polymerization of methacrylic acid (MAA) and trimethylpropane trimethacrylate (TRIM). Non-imprinted polymers (NIPs) were produced as control by removing the template from the reaction media. The selective membrane was prepared by dispersing MIP or NIP particles in plasticizer and poly(vinyl chloride), PVC, and casting this mixture over a solid contact support made of graphite. The composition of the selective membrane was investigated with regard to kind/amount of sensory material (MIP or NIP), and the need for a lipophilic additive. Overall, MIP sensors with additive exhibited the best performance, with near-Nernstian response down to ~ 1 × 10− 4 mol L− 1, at pH 5, and a detection limitof ~ 8 × 10− 5 mol L− 1. Suitable selectivity was found for all membranes, assessed by the matched potential method against some of the most common species in urine (urea, sodium, creatinine, sulfate, fructose and hemoglobin). CRT selective membranes including MIP materials were applied successfully to the potentiometric determination of CRT in urine samples.

Inoculation with Metal-Mobilizing Plant-GrowthPromoting Rhizobacterium Bacillus sp. SC2b and Its Role in Rhizoremediation

A plant growth-promoting bacterial (PGPB) strain SC2b was isolated from the rhizosphere of Sedum plumbizincicola grown in lead (Pb)/zinc (Zn) mine soils and characterized as Bacillus sp. based on (1) morphological and biochemical characteristics and (2) partial 16S ribosomal DNA sequencing analysis. Strain SC2b exhibited high levels of resistance to cadmium (Cd) (300 mg/L), Zn (730 mg/L), and Pb (1400 mg/L). This strain also showed various plant growth-promoting (PGP) features such as utilization of 1-aminocyclopropane-1-carboxylate, solubilization of phosphate, and production of indole-3-acetic acid and siderophore. The strain mobilized high concentration of heavy metals from soils and exhibited different biosorption capacity toward the tested metal ions. Strain SC2b was further assessed for PGP activity by phytagar assay with a model plant Brassica napus. Inoculation of SC2b increased the biomass and vigor index of B. napus. Considering such potential, a pot experiment was conducted to assess the effects of inoculating the metal-resistant PGPB SC2b on growth and uptake of Cd, Zn and Pb by S. plumbizincicola in metal-contaminated agricultural soils. Inoculation with SC2b elevated the shoot and root biomass and leaf chlorophyll content of S. plumbizincicola. Similarly, plants inoculated with SC2b demonstrated markedly higher Cd and Zn accumulation in the root and shoot system, indicating that SC2b enhanced Cd and Zn uptake by S. plumbizincicola through metal mobilization or plant-microbial mediated changes in chemical or biological soil properties. Data demonstrated that the PGPB Bacillus sp. SC2b might serve as a future biofertilizer and an effective metal mobilizing bioinoculant for rhizoremediation of metal polluted soils.