Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols

A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.

Development of molecularly imprinted polymers using supercritical fluid technology

Dissertação para obtenção do Grau de Doutor em Química Sustentável

Energy-aware task mapping onto heterogeneous platforms using DVFS and sleep states

Heterogeneous multicore platforms are becoming an interesting alternative for embedded computing systems with limited power supply as they can execute specific tasks in an efficient manner. Nonetheless, one of the main challenges of such platforms consists of optimising the energy consumption in the presence of temporal constraints. This paper addresses the problem of task-to-core allocation onto heterogeneous multicore platforms such that the overall energy consumption of the system is minimised. To this end, we propose a two-phase approach that considers both dynamic and leakage energy consumption: (i) the first phase allocates tasks to the cores such that the dynamic energy consumption is reduced; (ii) the second phase refines the allocation performed in the first phase in order to achieve better sleep states by trading off the dynamic energy consumption with the reduction in leakage energy consumption. This hybrid approach considers core frequency set-points, tasks energy consumption and sleep states of the cores to reduce the energy consumption of the system. Major value has been placed on a realistic power model which increases the practical relevance of the proposed approach. Finally, extensive simulations have been carried out to demonstrate the effectiveness of the proposed algorithm. In the best-case, savings up to 18% of energy are reached over the first fit algorithm, which has shown, in previous works, to perform better than other bin-packing heuristics for the target heterogeneous multicore platform.

Protein-responsive polymers for point-of-care detection of cardiac biomarker

This work describes a novel use for the polymeric film, poly(o-aminophenol) (PAP) that was made responsive to a specific protein. This was achieved through templated electropolymerization of aminophenol (AP) in the presence of protein. The procedure involved adsorbing protein on the electrode surface and thereafter electroploymerizing the aminophenol. Proteins embedded at the outer surface of the polymeric film were digested by proteinase K and then washed away thereby creating vacant sites. The capacity of the template film to specifically rebind protein was tested with myoglobin (Myo), a cardiac biomarker for ischemia. The films acted as biomimetic artificial antibodies and were produced on a gold (Au) screen printed electrode (SPE), as a step towards disposable sensors to enable point-of-care applications. Raman spectroscopy was used to follow the surface modification of the Au-SPE. The ability of the material to rebind Myo was measured by electrochemical techniques, namely electrochemical impedance spectroscopy (EIS) and square wave voltammetry (SWV). The devices displayed linear responses to Myo in EIS and SWV assays down to 4.0 and 3.5 μg/mL, respectively, with detection limits of 1.5 and 0.8 μg/mL. Good selectivity was observed in the presence of troponin T (TnT) and creatine kinase (CKMB) in SWV assays, and accurate results were obtained in applications to spiked serum. The sensor described in this work is a potential tool for screening Myo in point-of-care due to the simplicity of fabrication, disposability, short time response, low cost, good sensitivity and selectivity.

Label-free Detection of Microcystin-LR in Waters Using Real-Time Potentiometric Biosensors Based on Single-Walled Carbon Nanotubes Imprinted Polymers

Microcystin-LR (MC-LR) is a dangerous toxin found in environmental waters, quantified by high performance liquid chromatography and/or enzyme-linked immunosorbent assays. Quick, low cost and on-site analysis is thus required to ensure human safety and wide screening programs. This work proposes label-free potentiometric sensors made of solid-contact electrodes coated with a surface imprinted polymer on the surface of Multi-Walled Carbon NanoTubes (CNTs) incorporated in a polyvinyl chloride membrane. The imprinting effect was checked by using non-imprinted materials. The MC-LR sensitive sensors were evaluated, characterized and applied successfully in spiked environmental waters. The presented method offered the advantages of low cost, portability, easy operation and suitability for adaptation to flow methods.

Determination of Microcystin-LR in waters in the subnanomolar range by sol–gel imprinted polymers on solid contact electrodes

The present work reports new sensors for the direct determination of Microcystin-LR (MC-LR) in environmental waters. Both selective membrane and solid contact were optimized to ensure suitable analytical features in potentiometric transduction. The sensing layer consisted of Imprinted Sol–Gel (ISG) materials capable of establishing surface interactions with MC-LR. Non-Imprinted Sol–Gel (NISG) membranes were used as negative control. The effects of an ionic lipophilic additive, time of sol–gel polymerization, time of extraction of MC-LR from the sensitive layer, and pH were also studied. The solid contact was made of carbon, aluminium, titanium, copper or nickel/chromium alloys (80 : 20 or 90 : 10). The best ISG sensor had a carbon solid contact and displayed average slopes of 211.3 mV per decade, with detection limits of 7.3 1010 M, corresponding to 0.75 mg L1 . It showed linear responses in the range of 7.7 1010 to 1.9 109 M of MC-LR (corresponding to 0.77–2.00 mg L1 ), thus including the limiting value for MC-LR in waters (1.0 mg L1 ). The potentiometric-selectivity coefficients were assessed by the matched potential method for ionic species regularly found in waters up to their limiting levels. Chloride (Cl) showed limited interference while aluminium (Al3+), ammonium (NH4 + ), magnesium (Mg2+), manganese (Mn2+), sodium (Na+ ), and sulfate (SO4 2) were unable to cause the required potential change. Spiked solutions were tested with the proposed sensor. The relative errors and standard deviation obtained confirmed the accuracy and precision of the method. It also offered the advantages of low cost, portability, easy operation and suitability for adaptation to flow methods.

Biomimetic sensors of molecularly-imprinted polymers for chlorpromazine determination

A new man-tailored biomimetic sensor for Chlorpromazine host-guest interactions and potentiometric transduction is presented. The artificial host was imprinted within methacrylic acid, 2-vinyl pyridine and 2-acrylamido-2-methyl-1-propanesulfonic acid based polymers. Molecularly imprinted particles were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. Slopes and detection limits ranged 51–67 mV/decade and 0.46–3.9 μg/mL, respectively, in steady state conditions. Sensors were independent from the pH of test solutions within 2.0–5.5. Good selectivity was observed towards oxytetracycline, doxytetracycline, ciprofloxacin, enrofloxacin, nalidixic acid, sulfadiazine, trimethoprim, glycine, hydroxylamine, cysteine and creatinine. Analytical features in flowing media were evaluated on a double-channel manifold, with a carrier solution of 5.0 × 10−2 mol/L phosphate buffer. Near-Nernstian response was observed over the concentration range 1.0 × 10−4 to 1.0 × 10−2 mol/L. Average slopes were about 48 mV/decade. The sensors were successfully applied to field monitoring of CPZ in fish samples, offering the advantages of simplicity, accuracy, automation feasibility and applicability to complex samples.

Trimethoprim-selective electrodes with molecularly imprinted polymers acting as ionophores and potentiometric transduction on graphite solid-contact

This work proposes a new biomimetic sensor material for trimethoprim. It is prepared by means of radical polymerization, having trimethylolpropane trimethacrylate as cross-linker, benzoyl peroxide as radicalar iniciator, chloroform as porogenic solvent, and methacrylic acid and 2-vinyl pyridine as monomers. Different percentages of sensor in a range between 1 and 6% were studied. Their behavior was compared to that obtained with ion-exchanger quaternary ammonium salt (additive tetrakis(p-chlorophenyl)borate or tetraphenylborate). The effect of an anionic additive in the sensing membrane was also tested. Trimethoprim sensors with 1% of imprinted particles from methacrylic acid monomers showed the best response in terms of slope (59.7 mV/decade) and detection limit (4.01 × 10− 7 mol/L). These electrodes displayed also a good selectivity towards nickel, manganese aluminium, ammonium, lead, potassium, sodium, iron, chromium, sulfadiazine, alanine, cysteine, tryptophan, valine and glycine. The sensors were not affected by pH changes from 2 to 6. They were successfully applied to the analysis of water from aquaculture.

New sensing materials of molecularly-imprinted polymers for the selective recognition of Chlortetracycline

As a result of the stressful conditions in aquaculture facilities there is a high risk of bacterial infections among cultured fish. Chlortetracycline (CTC) is one of the antimicrobials used to solve this problem. It is a broad spectrum antibacterial active against a wide range of Gram-positive and Gram-negative bacteria. Numerous analytical methods for screening, identifying, and quantifying CTC in animal products have been developed over the years. An alternative and advantageous method should rely on expeditious and efficient procedures providing highly specific and sensitive measurements in food samples. Ion-selective electrodes (ISEs) could meet these criteria. The only ISE reported in literature for this purpose used traditional electro-active materials. A selectivity enhancement could however be achieved after improving the analyte recognition by molecularly imprinted polymers (MIPs). Several MIP particles were synthesized and used as electro-active materials. ISEs based in methacrylic acid monomers showed the best analytical performance according to slope (62.5 and 68.6 mV/decade) and detection limit (4.1 × 10−5 and 5.5 × 10−5 mol L−1). The electrodes displayed good selectivity. The ISEs are not affected by pH changes ranging from 2.5 to 13. The sensors were successfully applied to the analysis of serum, urine and fish samples.

Energy-aware Task Allocation onto Unrelated Heterogeneous Multicore Platform for Mixed Criticality Systems

Presented at Work in Progress Session, IEEE Real-Time Systems Symposium (RTSS 2015). 1 to 4, Dec, 2015. San Antonio, U.S.A..

An integration bridge for heterogeneous e-service environments

Dissertação para obtenção do Grau de Mestre em Engenharia Electrotécnica e de Computadores

Measuring data transfer in heterogeneous IoT environments

Dissertação para obtenção do Grau de Mestre em Engenharia Electrotécnica e de Computadores

Organising interoperability information on highly dynamic and heterogeneous environments

Dissertação para obtenção do Grau de Mestre em Engenharia Electrotécnica e de Computadores

Waste collection routing-limited multiple landfills and heterogeneous fleet

This article deals with a real-life waste collection routing problem. To efficiently plan waste collection, large municipalities may be partitioned into convenient sectors and only then can routing problems be solved in each sector. Three diverse situations are described, resulting in three different new models. In the first situation, there is a single point of waste disposal from where the vehicles depart and to where they return. The vehicle fleet comprises three types of collection vehicles. In the second, the garage does not match any of the points of disposal. The vehicle is unique and the points of disposal (landfills or transfer stations) may have limitations in terms of the number of visits per day. In the third situation, disposal points are multiple (they do not coincide with the garage), they are limited in the number of visits, and the fleet is composed of two types of vehicles. Computational results based not only on instances adapted from the literature but also on real cases are presented and analyzed. In particular, the results also show the effectiveness of combining sectorization and routing to solve waste collection problems.

PIASA: A power and interference aware resource management strategy for heterogeneous workloads in cloud data centers

Cloud data centers have been progressively adopted in different scenarios, as reflected in the execution of heterogeneous applications with diverse workloads and diverse quality of service (QoS) requirements. Virtual machine (VM) technology eases resource management in physical servers and helps cloud providers achieve goals such as optimization of energy consumption. However, the performance of an application running inside a VM is not guaranteed due to the interference among co-hosted workloads sharing the same physical resources. Moreover, the different types of co-hosted applications with diverse QoS requirements as well as the dynamic behavior of the cloud makes efficient provisioning of resources even more difficult and a challenging problem in cloud data centers. In this paper, we address the problem of resource allocation within a data center that runs different types of application workloads, particularly CPU- and network-intensive applications. To address these challenges, we propose an interference- and power-aware management mechanism that combines a performance deviation estimator and a scheduling algorithm to guide the resource allocation in virtualized environments. We conduct simulations by injecting synthetic workloads whose characteristics follow the last version of the Google Cloud tracelogs. The results indicate that our performance-enforcing strategy is able to fulfill contracted SLAs of real-world environments while reducing energy costs by as much as 21%.