Novel potentiometric sensors of molecular imprinted polymers for specific binding of chlormequat

Molecularly imprinted polymers (MIP) were used as potentiometric sensors for the selective recognition and determination of chlormequat (CMQ). They were produced after radical polymerization of 4-vinyl pyridine (4-VP) or methacrylic acid (MAA) monomers in the presence of a cross-linker. CMQwas used as template. Similar nonimprinted (NI) polymers (NIP) were produced by removing the template from reaction media. The effect of kind and amount of MIP or NIP sensors on the potentiometric behavior was investigated. Main analytical features were evaluated in steady and flow modes of operation. The sensor MIP/4-VP exhibited the best performance, presenting fast near-Nernstian response for CMQover the concentration range 6.2×10-6 – 1.0×10-2 mol L-1 with detection limits of 4.1×10-6 mol L-1. The sensor was independent from the pH of test solutions in the range 5 – 10. Potentiometric selectivity coefficients of the proposed sensors were evaluated over several inorganic and organic cations. Results pointed out a good selectivity to CMQ. The sensor was applied to the potentiometric determination of CMQin commercial phytopharmaceuticals and spiked water samples. Recoveries ranged 96 to 108.5%.

Heterogeneous kinetics of the reduction of chromium (VI) by elemental iron

Zero valent iron (ZVI) has been extensively used as a reactive medium for the reduction of Cr(VI) to Cr(III) in reactive permeable barriers. The kinetic rate depends strongly on the superficial oxidation of the iron particles used and the preliminary washing of ZVI increases the rate. The reaction has been primarily modelled using a pseudo-first-order kinetics which is inappropriate for a heterogeneous reaction. We assumed a shrinking particle type model where the kinetic rate is proportional to the available iron surface area, to the initial volume of solution and to the chromium concentration raised to a power ˛ which is the order of the chemical reaction occurring at surface. We assumed α= 2/3 based on the likeness to the shrinking particle models with spherical symmetry. Kinetics studies were performed in order to evaluate the suitability of this approach. The influence of the following parameters was experimentally studied: initial available surface area, chromium concentration, temperature and pH. The assumed order for the reaction was confirmed. In addition, the rate constant was calculated from data obtained in different operating conditions. Digital pictures of iron balls were periodically taken and the image treatment allowed for establishing the time evolution of their size distribution.

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 fromthe pHof test solutionswithin 2.0–5.5.Good selectivitywas 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.

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.

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.

On the adaptation of broadcast transactions in token-passing fieldbus networks with heterogeneous transmission media

Broadcast networks that are characterised by having different physical layers (PhL) demand some kind of traffic adaptation between segments, in order to avoid traffic congestion in linking devices. In many LANs, this problem is solved by the actual linking devices, which use some kind of flow control mechanism that either tell transmitting stations to pause (the transmission) or just discard frames. In this paper, we address the case of token-passing fieldbus networks operating in a broadcast fashion and involving message transactions over heterogeneous (wired or wireless) physical layers. For the addressed case, real-time and reliability requirements demand a different solution to the traffic adaptation problem. Our approach relies on the insertion of an appropriate idle time before a station issuing a request frame. In this way, we guarantee that the linking devices’ queues do not increase in a way that the timeliness properties of the overall system turn out to be unsuitable for the targeted applications.

Assigning real-time tasks on heterogeneous multiprocessors with two unrelated types of processors

A preliminary version of this paper appeared in Proceedings of the 31st IEEE Real-Time Systems Symposium, 2010, pp. 239–248.

A PTAS for assigning sporadic tasks on two-type heterogeneous multiprocessors

Consider the problem of determining a task-toprocessor assignment for a given collection of implicit-deadline sporadic tasks upon a multiprocessor platform in which there are two distinct kinds of processors. We propose a polynomialtime approximation scheme (PTAS) for this problem. It offers the following guarantee: for a given task set and a given platform, if there exists a feasible task-to-processor assignment, then given an input parameter, ϵ, our PTAS succeeds, in polynomial time, in finding such a feasible task-to-processor assignment on a platform in which each processor is 1+3ϵ times faster. In the simulations, our PTAS outperforms the state-of-the-art PTAS [1] and also for the vast majority of task sets, it requires significantly smaller processor speedup than (its upper bound of) 1+3ϵ for successfully determining a feasible task-to-processor assignment.

Energy-conscious tasks partitioning onto a heterogeneous multi-core platform

Modern multicore processors for the embedded market are often heterogeneous in nature. One feature often available are multiple sleep states with varying transition cost for entering and leaving said sleep states. This research effort explores the energy efficient task-mapping on such a heterogeneous multicore platform to reduce overall energy consumption of the system. This is performed in the context of a partitioned scheduling approach and a very realistic power model, which improves over some of the simplifying assumptions often made in the state-of-the-art. The developed heuristic consists of two phases, in the first phase, tasks are allocated to minimise their active energy consumption, while the second phase trades off a higher active energy consumption for an increased ability to exploit savings through more efficient sleep states. Extensive simulations demonstrate the effectiveness of the approach.

Task assignment algorithms for two-type heterogeneous multiprocessors

Consider the problem of assigning real-time tasks on a heterogeneous multiprocessor platform comprising two different types of processors — such a platform is referred to as two-type platform. We present two linearithmic timecomplexity algorithms, SA and SA-P, each providing the follow- ing guarantee. For a given two-type platform and a given task set, if there exists a feasible task-to-processor-type assignment such that tasks can be scheduled to meet deadlines by allowing them to migrate only between processors of the same type, then (i) using SA, it is guaranteed to find such a feasible task-to- processor-type assignment where the same restriction on task migration applies but given a platform in which processors are 1+α/2 times faster and (ii) SA-P succeeds in finding 2 a feasible task-to-processor assignment where tasks are not allowed to migrate between processors but given a platform in which processors are 1+α/times faster, where 0<α≤1. The parameter α is a property of the task set — it is the maximum utilization of any task which is less than or equal to 1.

Provably good scheduling of sporadic tasks with resource sharing on a two-type heterogeneous multiprocessor platform

Consider the problem of scheduling a set of implicit-deadline sporadic tasks to meet all deadlines on a two-type heterogeneous multiprocessor platform where a task may request at most one of |R| shared resources. There are m1 processors of type-1 and m2 processors of type-2. Tasks may migrate only when requesting or releasing resources. We present a new algorithm, FF-3C-vpr, which offers a guarantee that if a task set is schedulable to meet deadlines by an optimal task assignment scheme that only allows tasks to migrate when requesting or releasing a resource, then FF-3Cvpr also meets deadlines if given processors 4+6*ceil(|R|/min(m1,m2)) times as fast. As far as we know, it is the first result for resource sharing on heterogeneous platforms with provable performance.

A conjecture about provably good task assignment on heterogeneous multiprocessor platforms but with a stronger adversary

Consider the problem of scheduling a set of implicit-deadline sporadic tasks to meet all deadlines on a heterogeneous multiprocessor platform. We use an algorithm proposed in [1] (we refer to it as LP-EE) from state-of-the-art for assigning tasks to heterogeneous multiprocessor platform and (re-)prove its performance guarantee but for a stronger adversary.We conjecture that if a task set can be scheduled to meet deadlines on a heterogeneous multiprocessor platform by an optimal task assignment scheme that allows task migrations then LP-EE meets deadlines as well with no migrations if given processors twice as fast. We illustrate this with an example.

Two-type heterogeneous multiprocessor scheduling: Is there a phase transition? (Extended Abstract)

Consider the problem of non-migratively scheduling a set of implicit-deadline sporadic tasks to meet all deadlines on a two-type heterogeneous multiprocessor platform. We ask the following question: Does there exist a phase transition behavior for the two-type heterogeneous multiprocessor scheduling problem? We also provide some initial observations via simulations performed on randomly generated task sets.

Provably good task assignment on heterogeneous multiprocessor platforms for a restricted case but with a stronger adversary

Consider the problem of scheduling a set of implicit-deadline sporadic tasks to meet all deadlines on a heterogeneous multiprocessor platform. We consider a restricted case where the maximum utilization of any task on any processor in the system is no greater than one. We use an algorithm proposed in [1] (we refer to it as LP-EE) from state-of-the-art for assigning tasks to heterogeneous multiprocessor platform and (re-)prove its performance guarantee for this restricted case but for a stronger adversary. We show that if a task set can be scheduled to meet deadlines on a heterogeneous multiprocessor platform by an optimal task assignment scheme that allows task migrations then LP-EE meets deadlines as well with no migrations if given processors twice as fast.

Intra-type migrative scheduling of implicit-deadline sporadic tasks on two- type heterogeneous multiprocessor

Consider the problem of scheduling a set of implicit-deadline sporadic tasks to meet all deadlines on a two-type heterogeneous multiprocessor platform. Each processor is either of type-1 or type-2 with each task having different execution time on each processor type. Jobs can migrate between processors of same type (referred to as intra-type migration) but cannot migrate between processors of different types. We present a new scheduling algorithm namely, LP-Relax(THR) which offers a guarantee that if a task set can be scheduled to meet deadlines by an optimal task assignment scheme that allows intra-type migration then LP-Relax(THR) meets deadlines as well with intra-type migration if given processors 1/THR as fast (referred to as speed competitive ratio) where THR <= 2/3.