Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Optimization of a microplate-based assay to assess esterase activity in the alga Pseudokirchneriella subcapitata

The present work describes the optimization of a short-term assay, based on the inhibition of the esterase activity of the alga Pseudokirchneriella subcapitata, in a microplate format. The optimization of the staining procedure showed that the incubation of the algal cells with 20 μmolL−1 fluorescein diacetate (FDA) for 40 min allowed discrimination between metabolic active and inactive cells. The shortterm assay was tested using Cu as toxicant. For this purpose, algal cells, in the exponential or stationary phase of growth, were exposed to the heavy metal in growing conditions. After 3 or 6 h, cells were subsequently stained with FDA, using the optimized procedure. For Cu, the 3- and 6-h EC50 values, based on the inhibition of the esterase activity of algal cells in the exponential phase of growth, were 209 and 130 μg L−1, respectively. P. subcapitata cells, in the stationary phase of growth, displayed higher effective concentration values than those observed in the exponential phase. The 3- and 6-h EC50 values for Cu, for cells in the stationary phase, were 443 and 268 μgL−1, respectively. This short-term microplate assay showed to be a rapid endpoint for testing toxicity using the alga P. subcapitata. The small volume required, the simplicity of the assay (no washing steps), and the automatic reading of the fluorescence make the assay particularly well suited for the evaluation of the toxicity of a high number of environmental samples.

Demand response management in power systems using a particle swarm optimization approach

Competitive electricity markets have arisen as a result of power-sector restructuration and power-system deregulation. The players participating in competitive electricity markets must define strategies and make decisions using all the available information and business opportunities.

Friction losses of Newtonian and non-Newtonian fluids flowing in laminar regime in a helical coil

This study aimed to carry out experimental work to determine, for Newtonian and non-Newtonian fluids, the friction factor (fc) with simultaneous heat transfer, at constant wall temperature as boundary condition, in fully developed laminar flow inside a vertical helical coil. The Newtonian fluids studied were aqueous solutions of glycerol, 25%, 36%, 43%, 59% and 78% (w/w). The non-Newtonian fluids were aqueous solutions of carboxymethylcellulose (CMC), a polymer, with concentrations of 0.2%, 0.3%, 0.4% and 0.6% (w/w) and aqueous solutions of xanthan gum (XG), another polymer, with concentrations of 0.1% and 0.2% (w/w). According to the rheological study done, the polymer solutions had shear-thinning behavior and different values of viscoelasticity. The helical coil used has an internal diameter, curvature ratio, length and pitch, respectively: 0.00483 m, 0.0263, 5.0 m and 11.34 mm. It was concluded that the friction factors, with simultaneous heat transfer, for Newtonian fluids can be calculated using expressions from literature for isothermal flows. The friction factors for CMC and XG solutions are similar to those for Newtonian fluids when the Dean number, based in a generalized Reynolds number, is less than 80. For Dean numbers higher than 80, the friction factors of the CMC solutions are lower those of the XG solutions and of the Newtonian fluids. In this range the friction factors decrease with the increase of the viscometric component of the solution and increase for increasing elastic component. The change of behavior at Dean number 80, for Newtonian and non-Newtonian fluids, is in accordance with the study of Ali [4]. There is a change of behavior at Dean number 80, for Newtonian and non-Newtonian fluids, which is in according to previous studies. The data also showed that the use of the bulk temperature or of the film temperature to calculate the physical properties of the fluid has a residual effect in the friction factor values.

Heat transfer coefficients from Newtonian and non-Newtonian fluids flowing in laminar regime in a helical coil

This study aimed to carry out experimental work to obtain, for Newtonian and non-Newtonian fluids, heat transfer coefficients, at constant wall temperature as boundary condition, in fully developed laminar flow inside a helical coil. The Newtonian fluids studied were aqueous solutions of glycerol, 25%, 36%, 43%, 59% and 78% (w/w) and the non-Newtonian fluids aqueous solutions of carboxymethylcellulose (CMC), a polymer, with concentrations 0.1%, 0.2%, 0.3%, 0.4% and 0.6% (w/w) and aqueous solutions of xanthan gum (XG), another polymer, with concentrations 0.1% and 0.2% (w/w). According to the rheological study performed, the polymer solutions had shear thinning behavior and different values of elasticity. The helical coil used has internal diameter, curvature ratio, length and pitch, respectively: 0.004575 m, 0.0263, 5.0 m and 11.34 mm. The Nusselt numbers for the CMC solutions are, on average, slightly higher than those for Newtonian fluids, for identical Prandtl and generalized Dean numbers. As outcome, the viscous component of the shear thinning polymer tends to potentiate the mixing effect of the Dean cells. The Nusselt numbers of the XG solutions are significant lower than those of the Newtonian solutions, for identical Prandtl and generalized Dean numbers. Therefore, the elastic component of the polymer tends to diminish the mixing effect of the Dean cells. A global correlation, for Nusselt number as a function of Péclet, generalized Dean and Weissenberg numbers for all Newtonian and non-Newtonian solutions studied, is presented.

Anti-tumoral effect of the non-nucleoside DNMT inhibitor RG108 in human prostate cancer cells

Background: Current therapeutic strategies for advanced prostate cancer (PCa) are largely ineffective. Because aberrant DNA methylation associated with inappropriate gene-silencing is a common feature of PCa, DNA methylation inhibitors might constitute an alternative therapy. In this study we aimed to evaluate the anti-cancer properties of RG108, a novel non-nucleoside inhibitor of DNA methyltransferases (DNMT), in PCa cell lines. Methods: The anti-tumoral impact of RG108 in LNCaP, 22Rv1, DU145 and PC-3 cell lines was assessed through standard cell viability, apoptosis and cell cycle assays. Likewise, DNMT activity, DNMT1 expression and global levels of DNA methylation were evaluated in the same cell lines. The effectiveness of DNA demethylation was further assessed through the determination of promoter methylation and transcript levels of GSTP1, APC and RAR-β2, by quantitative methylation-specific PCR and RT-PCR, respectively. Results: RG108 led to a significant dose and time dependent growth inhibition and apoptosis induction in LNCaP, 22Rv1 and DU145. LNCaP and 22Rv1 also displayed decreased DNMT activity, DNMT1 expression and global DNA methylation. Interestingly, chronic treatment with RG108 significantly decreased GSTP1, APC and RAR-β2 promoter hypermethylation levels, although mRNA re-expression was only attained GSTP1 and APC. Conclusions: RG108 is an effective tumor growth suppressor in most PCa cell lines tested. This effect is likely mediated by reversion of aberrant DNA methylation affecting cancer related-genes epigenetically silenced in PCa. However, additional mechanism might underlie the anti-tumor effects of RG108. In vivo studies are now mandatory to confirm these promising results and evaluate the potential of this compound for PCa therapy.

Convex optimization framework for intermediate deadline assignment in soft and hard real-time distributed systems

It is generally challenging to determine end-to-end delays of applications for maximizing the aggregate system utility subject to timing constraints. Many practical approaches suggest the use of intermediate deadline of tasks in order to control and upper-bound their end-to-end delays. This paper proposes a unified framework for different time-sensitive, global optimization problems, and solves them in a distributed manner using Lagrangian duality. The framework uses global viewpoints to assign intermediate deadlines, taking resource contention among tasks into consideration. For soft real-time tasks, the proposed framework effectively addresses the deadline assignment problem while maximizing the aggregate quality of service. For hard real-time tasks, we show that existing heuristic solutions to the deadline assignment problem can be incorporated into the proposed framework, enriching their mathematical interpretation.

Non pre-emptive scheduling of messages on SMTV token-passing networks

Fieldbus communication networks aim to interconnect sensors, actuators and controllers within distributed computer-controlled systems. Therefore, they constitute the foundation upon which real-time applications are to be implemented. A specific class of fieldbus communication networks is based on a simplified version of token-passing protocols, where each station may transfer, at most, a single message per token visit (SMTV). In this paper, we establish an analogy between non-preemptive task scheduling in single processors and the scheduling of messages on SMTV token-passing networks. Moreover, we clearly show that concepts such as blocking and interference in non-preemptive task scheduling have their counterparts in the scheduling of messages on SMTV token-passing networks. Based on this task/message scheduling analogy, we provide pre-run-time schedulability conditions for supporting real-time messages with SMTV token-passing networks. We provide both utilisation-based and response time tests to perform the pre-run-time schedulability analysis of real-time messages on SMTV token-passing networks, considering RM/DM (rate monotonic/deadline monotonic) and EDF (earliest deadline first) priority assignment schemes

Preemption delay analysis for floating non-preemptive region scheduling

In real-time systems, there are two distinct trends for scheduling task sets on unicore systems: non-preemptive and preemptive scheduling. Non-preemptive scheduling is obviously not subject to any preemption delay but its schedulability may be quite poor, whereas fully preemptive scheduling is subject to preemption delay, but benefits from a higher flexibility in the scheduling decisions. The time-delay involved by task preemptions is a major source of pessimism in the analysis of the task Worst-Case Execution Time (WCET) in real-time systems. Preemptive scheduling policies including non-preemptive regions are a hybrid solution between non-preemptive and fully preemptive scheduling paradigms, which enables to conjugate both world's benefits. In this paper, we exploit the connection between the progression of a task in its operations, and the knowledge of the preemption delays as a function of its progression. The pessimism in the preemption delay estimation is then reduced in comparison to state of the art methods, due to the increase in information available in the analysis.

An improved preemption delay upper bound for floating non-preemptive region

In embedded systems, the timing behaviour of the control mechanisms are sometimes of critical importance for the operational safety. These high criticality systems require strict compliance with the offline predicted task execution time. The execution of a task when subject to preemption may vary significantly in comparison to its non-preemptive execution. Hence, when preemptive scheduling is required to operate the workload, preemption delay estimation is of paramount importance. In this paper a preemption delay estimation method for floating non-preemptive scheduling policies is presented. This work builds on [1], extending the model and optimising it considerably. The preemption delay function is subject to a major tightness improvement, considering the WCET analysis context. Moreover more information is provided as well in the form of an extrinsic cache misses function, which enables the method to provide a solution in situations where the non-preemptive regions sizes are small. Finally experimental results from the implementation of the proposed solutions in Heptane are provided for real benchmarks which validate the significance of this work.

The utilization bound of non-preemptive rate-monotonic scheduling in controller area networks is 25%

Consider a distributed computer system comprising many computer nodes, each interconnected with a controller area network (CAN) bus. We prove that if priorities to message streams are assigned using rate-monotonic (RM) and if the requested capacity of the CAN bus does not exceed 25% then all deadlines are met.

Online robust optimization framework for QoS guarantees in distributed soft real-time systems

In distributed soft real-time systems, maximizing the aggregate quality-of-service (QoS) is a typical system-wide goal, and addressing the problem through distributed optimization is challenging. Subtasks are subject to unpredictable failures in many practical environments, and this makes the problem much harder. In this paper, we present a robust optimization framework for maximizing the aggregate QoS in the presence of random failures. We introduce the notion of K-failure to bound the effect of random failures on schedulability. Using this notion we define the concept of K-robustness that quantifies the degree of robustness on QoS guarantee in a probabilistic sense. The parameter K helps to tradeoff achievable QoS versus robustness. The proposed robust framework produces optimal solutions through distributed computations on the basis of Lagrangian duality, and we present some implementation techniques. Our simulation results show that the proposed framework can probabilistically guarantee sub-optimal QoS which remains feasible even in the presence of random failures.

Competitive dynamics for behavior coordination in a joint transportation task

We address the problem of coordinating two non-holonomic mobile robots that move in formation while transporting a long payload. A competitive dynamics is introduced that gradually controls the activation and deactivation of individual behaviors. This process introduces (asymmetrical) hysteresis during behavioral switching. As a result behavioral oscillations, due to noisy information, are eliminated. Results in indoor environments show that if parameter values are chosen within reasonable ranges then, in spite of noise in the robots communi- cation and sensors, the overall robotic system works quite well even in cluttered environments. The robots overt behavior is stable and smooth.

Improvement of a filters method in a derivative free optimization

Constraints nonlinear optimization problems can be solved using penalty or barrier functions. This strategy, based on solving the problems without constraints obtained from the original problem, have shown to be e ective, particularly when used with direct search methods. An alternative to solve the previous problems is the lters method. The lters method introduced by Fletcher and Ley er in 2002, , has been widely used to solve problems of the type mentioned above. These methods use a strategy di erent from the barrier or penalty functions. The previous functions de ne a new one that combine the objective function and the constraints, while the lters method treat optimization problems as a bi-objective problems that minimize the objective function and a function that aggregates the constraints. Motivated by the work of Audet and Dennis in 2004, using lters method with derivative-free algorithms, the authors developed works where other direct search meth- ods were used, combining their potential with the lters method. More recently. In a new variant of these methods was presented, where it some alternative aggregation restrictions for the construction of lters were proposed. This paper presents a variant of the lters method, more robust than the previous ones, that has been implemented with a safeguard procedure where values of the function and constraints are interlinked and not treated completely independently.

Filters method in direct search optimization, new measures to admissibility

Constrained nonlinear optimization problems are usually solved using penalty or barrier methods combined with unconstrained optimization methods. Another alternative used to solve constrained nonlinear optimization problems is the lters method. Filters method, introduced by Fletcher and Ley er in 2002, have been widely used in several areas of constrained nonlinear optimization. These methods treat optimization problem as bi-objective attempts to minimize the objective function and a continuous function that aggregates the constraint violation functions. Audet and Dennis have presented the rst lters method for derivative-free nonlinear programming, based on pattern search methods. Motivated by this work we have de- veloped a new direct search method, based on simplex methods, for general constrained optimization, that combines the features of the simplex method and lters method. This work presents a new variant of these methods which combines the lters method with other direct search methods and are proposed some alternatives to aggregate the constraint violation functions.