Triphenylmethane dyes, an alternative for mediated electronic transfer systems in glucose oxidase biofuel cells

The bioelectrochemical behavior of three triphenylmethane (TPM) dyes commonly used as pH indicators, and their application in mediated electron transfer systems for glucose oxidase bioanodes in biofuel cells was investigated. Bromophenol Blue, Bromothymol Blue, Bromocresol Green were compared bio-electrochemically against two widely used mediators, benzoquinone and ferrocene carboxy aldehyde. Biochemical studies were performed in terms of enzymatic oxidation, enzyme affinity, catalytic efficiency and co-factor regeneration. The different features of the TPM dyes as mediators are determined by the characteristics in the oxidation/reduction processes studied electrochemically. The reversibility of the oxidation/reduction processes was also established through the dependence of the voltammetric peaks with the sweep rates. All three dyes showed good performances compared to the FA and BQ when evaluated in a half enzymatic fuel cell. Potentiodynamic and power response experiments showed maxima power densities of 32.8 mu W cm(-2) for ferrocene carboxy aldehyde followed by similar values obtained for TPM dyes around 30 mu W cm(-2) using glucose and mediator concentrations of 10 mmol L(-1) and 1.0 mmol L(-1), respectively. Since no mediator consumption was observed during the bioelectrochemical process, and also good redox re-cycled processes were achieved, the use of triphenylmethane dyes is considered to be promising compared to other mediated systems used with glucose oxiclase bioanodes and/or biofuel cells. (C) 2011 Elsevier Inc. All rights reserved.

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Structural and Electronic Properties of Dipyridamole and Derivatives

Quantum mechanical calculations at the B3LYP theory level, together with the 6-31G* basis set, were employed to obtain the energy, ionization potential, and polarizabilites for dipyridamole and derivatives, which are compared with their biological activity. Density functional calculations of the spin densities were performed for radical formed by electron abstraction of dipyridamole and derivatives. The unpaired electron remains in dipyridamole is localized on the nitrogen atoms in the substituent positions 1, 3, 5, 7, 11, 12, 13, 14, with participation of the 9 and 10 carbons in the pyrimido-pyrimidine ring. The antioxidant activity is related with ionization potential, polarizability and Log P.

Electronic synergism in [RuCl(2)(PPh(3))(2)(amine)] complexes differing the reactivity for ROMP of norbornene and norbornadiene

The reactivity of the new complex [RuCl(2)(PPh(3))(2)(3,5-Me(2)piperidine)], complex 1, was investigated for ring opening metathesis polymerization (ROMP) of norbornene (NBE) and norbornadiene (NBD) in the presence of ethyl diazoacetate (EDA) in CHCl(3). The aim is to observe the combination of PPh(3) and an amine as ancillary ligands concerning the steric hindrance and the electronic perturbation in the properties of the N-bound site when replacing the amines. Thus, the results with 1 were compared to the results obtained when the amine is piperidine (complex 2). Reaction with 1 provides 70% yield of isolated polyNBE (M(n) =8.3 x 10(4) g/mol; PDI = 2.03), whereas 2 provides quantitative reaction (M(n) = 1.2 x 10(5) g/mol; PDI = 1.90) with [NBE]/[Ru] = 5000, [EDA]/[Ru] = 48 and 1.1 mu mol of Ru for 5 min at 25 degrees C. The resulting polymers showed c.a. 62% of trans-polyNBE, determined by (1)H NMR, and T(g) = 32 degrees C, determined by DSC and DMTA. For ROMP of NBD, 1 showed quantitative yield with PDI =2.62 when [NBD]/[Ru] = 5000 for 20 min at 25 degrees C, whereas the reaction with 2 reached 55% with PDI = 2.16 in the same conditions. It is concluded that the presence of the two methyl groups in the piperidine ring provides an increase in the induction period to produce the Ru-carbene species justifying better polyNBE results with 2, and a greater amine(sigma)-> Ru(pi)-> monomer synergism which contributed to the best activation of less tensioned olefin as NBD. (C) 2010 Elsevier B.V. All rights reserved.

Electronic contracting in aircraft aftercare: A case study

Distributed systems comprised of autonomous self-interested entities require some sort of control mechanism to ensure the predictability of the interactions that drive them. This is certainly true in the aerospace domain, where manufacturers, suppliers and operators must coordinate their activities to maximise safety and profit, for example. To address this need, the notion of norms has been proposed which, when incorporated into formal electronic documents, allow for the specification and deployment of contract-driven systems. In this context, we describe the CONTRACT framework and architecture for exactly this purpose, and describe a concrete instantiation of this architecture as a prototype system applied to an aerospace aftercare scenario.

Handling Mitigating Circumstances for Electronic Contracts

Electronic contracts are a means of representing agreed responsibilities and expected behaviour of autonomous agents acting on behalf of businesses. They can be used to regulate behaviour by providing negative consequences, penalties, where the responsibilities and expectations are not met, i.e. the contract is violated. However, long-term business relationships require some flexibility in the face of circumstances that do not conform to the assumptions of the contract, that is, mitigating circumstances. In this paper, we describe how contract parties can represent and enact policies on mitigating circumstances. As part of this, we require records of what has occurred within the system leading up to a violation: the provenance of the violation. We therefore bring together contract-based and provenance systems to solve the issue of mitigating circumstances.

Towards a Formalisation of Electronic Contracting Environments

The IST-CONTRACT project is in the process of creating an electronic contracting language. One of the goals of this language is that it has formal underpinnings, and formalizations at a number of levels have been created. One of the lowest levels, upon which the other levels are built is the normative level. At this level, we identify how contract clauses (modeled as norms) may evolve over time. In this paper, we describe this formalization, and show how we may associate various states with a norm throughout its lifecycle. We also show how more complex evaluations may be carried out over a norm, and conclude with an example showing the application of the framework over a contract and its associated norms.

Determining the Trustworthiness of New Electronic Contracts

Expressing contractual agreements electronically potentially allows agents to automatically perform functions surrounding contract use: establishment, fulfilment, renegotiation etc. For such automation to be used for real business concerns, there needs to be a high level of trust in the agent-based system. While there has been much research on simulating trust between agents, there are areas where such trust is harder to establish. In particular, contract proposals may come from parties that an agent has had no prior interaction with and, in competitive business-to-business environments, little reputation information may be available. In human practice, trust in a proposed contract is determined in part from the content of the proposal itself, and the similarity of the content to that of prior contracts, executed to varying degrees of success. In this paper, we argue that such analysis is also appropriate in automated systems, and to provide it we need systems to record salient details of prior contract use and algorithms for assessing proposals on their content. We use provenance technology to provide the former and detail algorithms for measuring contract success and similarity for the latter, applying them to an aerospace case study.

Electronic Business Contracts between Services

Electronic contracts mirror the paper versions exchanged between businesses today, and offer the possibility of dynamic, automatic creation and enforcement of restrictions and compulsions on service behaviour that are designed to ensure business objectives are met. Where there are many contracts within a particular application, it can be difficult to determine whether the system can reliably fulfil them all, yet computer-parsable electronic contracts may allow such verification to be automated. In this chapter, we describe a conceptual framework and architecture specification in which normative business contracts can be electronically represented, verified, established, renewed, and so on. In particular, we aim to allow systems containing multiple contracts to be checked for conflicts and violations of business objectives. We illustrate the framework and architecture with an aerospace aftermarket example.

Using Normative Markov Decision Processes for Evaluating Electronic Contracts: A Case Study in a Simulated Aerospace Aftermarket

Before signing electronic contracts, a rational agent should estimate the expected utilities of these contracts and calculate the violation risks related to them. In order to perform such pre-signing procedures, this agent has to be capable of computing a policy taking into account the norms and sanctions in the contracts. In relation to this, the contribution of this work is threefold. First, we present the Normative Markov Decision Process, an extension of the Markov Decision Process for explicitly representing norms. In order to illustrate the usage of our framework, we model an example in a simulated aerospace aftermarket. Second, we specify an algorithm for identifying the states of the process which characterize the violation of norms. Finally, we show how to compute policies with our framework and how to calculate the risk of violating the norms in the contracts by adopting a particular policy.

Designing a Remote Navigation System

This project involves the design and implementation of a global electronic tracking system intended for use by trans-oceanic vessels, using the technology of the U.S. Government's Global Positioning System (GPS) and a wireless connection to a networked computer. Traditional navigation skills are being replaced with highly accurate electronics. GPS receivers, computers, and mobile communication are becoming common among both recreational and commercial boaters. With computers and advanced communication available throughout the maritime world, information can be shared instantaneously around the globe. This ability to monitor one's whereabouts from afar can provide an increased level of safety and efficiency. Current navigation software seldom includes the capability of providing upto-the-minute navigation information for remote display. Remote access to this data will allow boat owners to track the progress of their boats, land-based organizations to monitor weather patterns and suggest course changes, and school groups to track the progress of a vessel and learn about navigation and science. The software developed in this project allows navigation information from a vessel to be remotely transmitted to a land-based server, for interpretation and deployment to remote users over the Internet. This differs from current software in that it allows the tracking of one vessel by multiple users and provides a means for two-way text messaging between users and the vesseI. Beyond the coastal coverage provided by cellular telephones, mobile communication is advancing rapidly. Current tools such as satellite telephones and single-sideband radio enable worldwide communications, including the ability to connect to the Internet. If current trends continue, portable global communication will be available at a reasonable price and Internet connections on boats will become more common.