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%.

Electrochemical DNA-sensor for evaluation of total antioxidant capacity of flavours and flavoured waters using superoxide radical damage

In this paper, a biosensor based on a glassy carbon electrode (GCE) was used for the evaluation of the total antioxidant capacity (TAC) of flavours and flavoured waters. This biosensor was constructed by immobilising purine bases, guanine and adenine, on a GCE. Square wave voltammetry (SWV) was selected for the development of this methodology. Damage caused by the reactive oxygen species (ROS), superoxide radical (O2·−), generated by the xanthine/xanthine oxidase (XOD) system on the DNA-biosensor was evaluated. DNA-biosensor encountered with oxidative lesion when it was in contact with the O2·−. There was less oxidative damage when reactive antioxidants were added. The antioxidants used in this work were ascorbic acid, gallic acid, caffeic acid, coumaric acid and resveratrol. These antioxidants are capable of scavenging the superoxide radical and therefore protect the purine bases immobilized on the GCE surface. The results demonstrated that the DNA-based biosensor is suitable for the rapid assess of TAC in beverages.

Electrocatalytic evaluation of DNA damage by superoxide radical for antioxidant capacity assessment

The integrity of DNA purine bases was herein used to evaluate the antioxidant capacity. Unlike other DNA-based antioxidant sensors reported so far, the damaging agent chosen was the O 2 radical enzymatically generated by the xanthine/xanthine oxidase system. An adenine-rich oligonucleotide was adsorbed on carbon paste electrodes and subjected to radical damage in the presence/absence of several antioxidant compounds. As a result, partial damage on DNA was observed. A minor product of the radical oxidation was identified by cyclic voltammetry as a diimine adenine derivative also formed during the electrochemical oxidation of adenine/guanine bases. The protective efficiency of several antioxidant compounds was evaluated after electrochemical oxidation of the remaining unoxidized adenine bases, by measuring the electrocatalytic current of NADH mediated by the adsorbed catalyst species generated. A comparison between O 2 and OH radicals as a source of DNA lesions and the scavenging efficiency of various antioxidant compounds against both of them is discussed. Finally, the antioxidant capacity of beverages was evaluated and compared with the results obtained with an optical method.

Photostabilization of phenoxyacetic acid herbicides MCPA and mecoprop by hydroxypropyl-β-cyclodextrin

New strategies to reduce the environmental and economic costs of pesticides use are currently under study. Microencapsulation has been used as a versatile tool for the production of controlled release agricultural formulations. In this study, the photochemical degradation of the herbicides MCPA and mecoprop has been investigated in different aqueous media such as ultrapure and river water under simulated solar irradiation. To explore the possibility of introducing cyclodextrins in the herbicide formulations, the photodegradation study of the inclusion complexes of MCPA and mecoprop with (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) was also performed. The half-lives of MCPA and mecoprop inclusion complexes were increased approximately by a factor of three related to the free molecules. Additionally, it has been shown that the photodegradation of MCPA and mecoprop is influenced by their structural features. The additional methyl group existing in mecoprop molecular structure has a positive influence on the stabilization of the radical intermediate formed in the first stage of photodegradation of both herbicides. The results found indicated that MCPA and mecoprop form inclusion complexes with HP-β-CD showing higher photostability compared to free herbicides indicating that HP-β-CD may serve as ingredient in these herbicide formulations.

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.

A proposal for media component brokerage

This paper describes how MPEG-4 object based video (obv) can be used to allow selected objects to be inserted into the play-out stream to a specific user based on a profile derived for that user. The application scenario described here is for personalized product placement, and considers the value of this application in the current and evolving commercial media distribution market given the huge emphasis media distributors are currently placing on targeted advertising. This level of application of video content requires a sophisticated content description and metadata system (e.g., MPEG-7). The scenario considers the requirement for global libraries to provide the objects to be inserted into the streams. The paper then considers the commercial trading of objects between the libraries, video service providers, advertising agencies and other parties involved in the service. Consequently a brokerage of video objects is proposed based on negotiation and trading using intelligent agents representing the various parties. The proposed Media Brokerage Platform is a multi-agent system structured in two layers. In the top layer, there is a collection of coarse grain agents representing the real world players – the providers and deliverers of media contents and the market regulator profiler – and, in the bottom layer, there is a set of finer grain agents constituting the marketplace – the delegate agents and the market agent. For knowledge representation (domain, strategic and negotiation protocols) we propose a Semantic Web approach based on ontologies. The media components contents should be represented in MPEG-7 and the metadata describing the objects to be traded should follow a specific ontology. The top layer content providers and deliverers are modelled by intelligent autonomous agents that express their will to transact – buy or sell – media components by registering at a service registry. The market regulator profiler creates, according to the selected profile, a market agent, which, in turn, checks the service registry for potential trading partners for a given component and invites them for the marketplace. The subsequent negotiation and actual transaction is performed by delegate agents in accordance with their profiles and the predefined rules of the market.

B2B platform for media content personalisation

This paper proposes a novel business model to support media content personalisation: an agent-based business-to-business (B2B) brokerage platform for media content producer and distributor businesses. Distributors aim to provide viewers with a personalised content experience and producers wish to en-sure that their media objects are watched by as many targeted viewers as possible. In this scenario viewers and media objects (main programmes and candidate objects for insertion) have profiles and, in the case of main programme objects, are annotated with placeholders representing personalisation opportunities, i.e., locations for insertion of personalised media objects. The MultiMedia Brokerage (MMB) platform is a multiagent multilayered brokerage composed by agents that act as sellers and buyers of viewer stream timeslots and/or media objects on behalf of the registered businesses. These agents engage in negotiations to select the media objects that best match the current programme and viewer profiles.

Engineering PROFIBUS networks with heterogeneous transmission media

A significant number of process control and factory automation systems use PROFIBUS as the underlying fieldbus communication network. The process of properly setting up a PROFIBUS network is not a straightforward task. In fact, a number of network parameters must be set for guaranteeing the required levels of timeliness and dependability. Engineering PROFIBUS networks is even more subtle when the network includes various physical segments exhibiting heterogeneous specifications, such as bus speed or frame formats, just to mention a few. In this paper we provide underlying theory and a methodology to guarantee the proper operation of such type of heterogeneous PROFIBUS networks. We additionally show how the methodology can be applied to the practical case of PROFIBUS networks containing simultaneously DP (Decentralised Periphery) and PA (Process Automation) segments, two of the most used commercial-off-the-shelf (COTS) PROFIBUS solutions. The importance of the findings is however not limited to this case. The proposed methodology can be generalised to cover other heterogeneous infrastructures. Hybrid wired/wireless solutions are just an example for which an enormous eagerness exists.

Media Brokerage: Agent-Based SLA Negotiation

Media content personalisation is a major challenge involving viewers as well as media content producer and distributor businesses. The goal is to provide viewers with media items aligned with their interests. Producers and distributors engage in item negotiations to establish the corresponding service level agreements (SLA). In order to address automated partner lookup and item SLA negotiation, this paper proposes the MultiMedia Brokerage (MMB) platform, which is a multiagent system that negotiates SLA regarding media items on behalf of media content producer and distributor businesses. The MMB platform is structured in four service layers: interface, agreement management, business modelling and market. In this context, there are: (i) brokerage SLA (bSLA), which are established between individual businesses and the platform regarding the provision of brokerage services; and (ii) item SLA (iSLA), which are established between producer and distributor businesses about the provision of media items. In particular, this paper describes the negotiation, establishment and enforcement of bSLA and iSLA, which occurs at the agreement and negotiation layers, respectively. The platform adopts a pay-per-use business model where the bSLA define the general conditions that apply to the related iSLA. To illustrate this process, we present a case study describing the negotiation of a bSLA instance and several related iSLA instances. The latter correspond to the negotiation of the Electronic Program Guide (EPG) for a specific end viewer.

Desenvolvimento e aplicação de um biossensor para monitorização de creatinina, um biomarcador associado a doenças emergentes

Este trabalho descreve o desenvolvimento de um material sensor para creatinina por impressão molecular em estrutura polimérica (MIP) e a sua aplicação no desenvolvimento de um dispositivo de natureza potenciométrica para a determinação da molécula alvo em fluidos biológicos. A creatinina é um dos biomarcadores mais utilizados no acompanhamento da doença renal, já que é um bom indicador da taxa de filtração glomerular (TFG). Os materiais biomiméticos desenhados para interação com a creatinina foram obtidos por polimerização radicalar, recorrendo a monómeros de ácido metacríclico ou de vinilpiridina e a um agente de reticulação apropriado. De modo a aferir o efeito da impressão da creatinina na resposta dos materiais MIP à sua presença, foram também preparados e avaliados materiais de controlo, obtidos sem impressão molecular (NIP). O controlo da constituição química destes materiais, incluindo a extração da molécula impressa, foi realizado por Espectroscopia de Raman e de Infravermelho com Transformada de Fourrier. A afinidade de ligação entre estes materiais e a creatinina foi também avaliada com base em estudos cinéticos. Todos os materiais descritos foram integrados em membranas selectivas de elétrodos seletivos de ião, preparadas sem ou com aditivo iónico lipófilo, de carga negativa ou positiva. A avaliação das características gerais de funcionamento destes elétrodos, em meios de composição e pH diferentes, indicaram que as membranas com materiais impressos e aditivo aniónico eram as únicas com utilidade analítica. Os melhores resultados foram obtidos em solução tampão Piperazine-N,N′-bis(2- ethanesulfonic acid), PIPES, de pH 2,8, condição que permitiu obter uma resposta quasi-Nernstiana, a partir de 1,6×10-5 mol L-1. Estes elétrodos demonstraram ainda uma boa selectividade ao apresentaram uma resposta preferencial para a creatinina quando na presença de ureia, carnitina, glucose, ácido ascórbico, albumina, cloreto de cálcio, cloreto de potássio, cloreto de sódio e sulfato de magnésio. Os elétrodos foram ainda aplicados com sucesso na análise de amostras sintéticas de urina, quando os materiais sensores eram baseados em ácido metacrilico, e soro, quando os materiais sensores utilizados eram baseados em vinilpiridina.

Brokerage Platform for Media Content Recommendation

Near real time media content personalisation is nowadays a major challenge involving media content sources, distributors and viewers. This paper describes an approach to seamless recommendation, negotiation and transaction of personalised media content. It adopts an integrated view of the problem by proposing, on the business-to-business (B2B) side, a brokerage platform to negotiate the media items on behalf of the media content distributors and sources, providing viewers, on the business-to-consumer (B2C) side, with a personalised electronic programme guide (EPG) containing the set of recommended items after negotiation. In this setup, when a viewer connects, the distributor looks up and invites sources to negotiate the contents of the viewer personal EPG. The proposed multi-agent brokerage platform is structured in four layers, modelling the registration, service agreement, partner lookup, invitation as well as item recommendation, negotiation and transaction stages of the B2B processes. The recommendation service is a rule-based switch hybrid filter, including six collaborative and two content-based filters. The rule-based system selects, at runtime, the filter(s) to apply as well as the final set of recommendations to present. The filter selection is based on the data available, ranging from the history of items watched to the ratings and/or tags assigned to the items by the viewer. Additionally, this module implements (i) a novel item stereotype to represent newly arrived items, (ii) a standard user stereotype for new users, (iii) a novel passive user tag cloud stereotype for socially passive users, and (iv) a new content-based filter named the collinearity and proximity similarity (CPS). At the end of the paper, we present off-line results and a case study describing how the recommendation service works. The proposed system provides, to our knowledge, an excellent holistic solution to the problem of recommending multimedia contents.

Social Media Integration in Video Games: A Social Overlay for Desktop Games

Simpósio de Informática (INForum 2015), Covilhã, Portugal. Notes: Best paper award nominee.

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.

Ex-ante evaluation by the media of the Guimarães 2012 European Capital of Culture

The nomination of Guimarães to host the 2012 European Capital of Culture (ECC) has put on the agenda of the city the need of measuring the effects that the implementation of this mega event could have in it and in the municipality a whole. The balance of the benefits and costs and an extended community involvement tend to reduce negative impacts and enhance positive ones. This chapter analyzes the involvement of population and local associations in the planning and organization of the 2012 Guimarães European Capital of Culture, using the coverage made during 2011 by local and national press of the mega event. A content analysis of the news published covering the period between January and December 2011 and using three newspapers was conducted. From those, two were local and weekly newspapers and one was a national daily one. Looking to data results, it can be concluded that it was poor the community involvement and, also, the one of the cultural associations in the organizations of the 2012 ECC. A strong negative reaction to the model choose to plan the mega event conducted by official organizers was found, which has cast doubts on the desirable participation of the residents and, consequently, on the success of the mega event, especially in a perspective of a medium and long term effects.