Towards a reliable technology for antioxidant capacity and oxidative damage evaluation: Electrochemical (bio)sensors

To counteract and prevent the deleterious effect of free radicals the living organisms have developed complex endogenous and exogenous antioxidant systems. Several analytical methodologies have been proposed in order to quantify antioxidants in food, beverages and biological fluids. This paper revises the electroanalytical approaches developed for the assessment of the total or individual antioxidant capacity. Four electrochemical sensing approaches have been identified, based on the direct electrochemical detection of antioxidant at bare or chemically modified electrodes, and using enzymatic and DNA-based biosensors.

Control and comparison of the antioxidant capacity of beers

The purpose of the present work is to determine the antioxidant capacity (AC) of 27 commercial beers. The AC indicates the degree of protection of a certain organism against oxidative damage provoked by reactive oxygen and nitrogen species. Assays were carried out by the following methods: (i) total radical trapping antioxidant parameter (TRAP); (ii) trolox equivalent antioxidant capacity (TEAC); (iii) trolox equivalent antioxidant capacity (DPPH); (iv) ferric-ion reducing antioxidant parameter (FRAP); (v) cupric reducing antioxidant capacity (CUPRAC); (vi) oxygen radical absorbance capacity (ORAC). Ascorbic acid (AA), gallic acid (GA) and trolox (TR) were used as standards. All beers showed antioxidant power, but a wide range of ACs was observed. The effect of several factors upon these differences was studied. Statistical differences were found between ACs of beers of different colours. ORAC method provided always higher experimental ACs, of significant statistical differences to other assays.

Capacity sharing and stealing in serverbased real-time systems

A dynamic scheduler that supports the coexistence of guaranteed and non-guaranteed bandwidth servers is proposed. Overloads are handled by an efficient reclaiming of residual capacities originated by early completions as well as by allowing reserved capacity stealing of non-guaranteed bandwidth servers. The proposed dynamic budget accounting mechanism ensures that at a particular time the currently executing server is using a residual capacity, its own capacity or is stealing some reserved capacity, eliminating the need of additional server states or unbounded queues. The server to which the budget accounting is going to be performed is dynamically determined at the time instant when a capacity is needed. This paper describes and evaluates the proposed scheduling algorithm, showing that it can efficiently reduce the mean tardiness of periodic jobs. The achieved results become even more significant when tasks’ computation times have a large variance.

Differences of absorptive capacity between firms within a cluster

Firms located within a cluster have access to tacit, complex and specific local knowledge which allow them to develop competitive advantage. However, firms have no equal ability to access and to apply that knowledge, meaning that not all have a similar knowledge absorptive capacity. Using a sample of the largest Portuguese firms within a footwear cluster, this paper examine whether there are significant differences in firm’s absorptive capacity and whether such differences within a cluster are related to firms’ specific characteristics. The results suggest that absorptive capacity is significantly associated with the firms’ characteristics, namely size, export intensity and position within the cluster.

A capacity sharing and stealing strategy for open real-time systems

This paper focuses on the scheduling of tasks with hard and soft real-time constraints in open and dynamic real-time systems. It starts by presenting a capacity sharing and stealing (CSS) strategy that supports the coexistence of guaranteed and non-guaranteed bandwidth servers to efficiently handle soft-tasks’ overloads by making additional capacity available from two sources: (i) reclaiming unused reserved capacity when jobs complete in less than their budgeted execution time and (ii) stealing reserved capacity from inactive non-isolated servers used to schedule best-effort jobs. CSS is then combined with the concept of bandwidth inheritance to efficiently exchange reserved bandwidth among sets of inter-dependent tasks which share resources and exhibit precedence constraints, assuming no previous information on critical sections and computation times is available. The proposed Capacity Exchange Protocol (CXP) has a better performance and a lower overhead when compared against other available solutions and introduces a novel approach to integrate precedence constraints among tasks of open real-time systems.

On the capacity of cluster-tree ZigBee networks

Modeling the fundamental performance limits of Wireless Sensor Networks (WSNs) is of paramount importance to understand their behavior under worst-case conditions and to make the appropriate design choices. In that direction this paper contributes with an analytical methodology for modeling cluster-tree WSNs where the data sink can either be static or mobile. We assess the validity and pessimism of analytical model by comparing the worst-case results with the values measured through an experimental test-bed based on Commercial-Off- The-Shelf (COTS) technologies, namely TelosB motes running TinyOS.

Capacity sharing and stealing in dynamic server-based real-time systems

This paper proposes a dynamic scheduler that supports the coexistence of guaranteed and non-guaranteed bandwidth servers to efficiently handle soft-tasks’ overloads by making additional capacity available from two sources: (i) residual capacity allocated but unused when jobs complete in less than their budgeted execution time; (ii) stealing capacity from inactive non-isolated servers used to schedule best-effort jobs. The effectiveness of the proposed approach in reducing the mean tardiness of periodic jobs is demonstrated through extensive simulations. The achieved results become even more significant when tasks’ computation times have a large variance.

The capacity exchange protocol

This paper proposes a new strategy to integrate shared resources and precedence constraints among real-time tasks, assuming no precise information on critical sections and computation times is available. The concept of bandwidth inheritance is combined with a capacity sharing and stealing mechanism to efficiently exchange bandwidth among tasks to minimise the degree of deviation from the ideal system’s behaviour caused by inter-application blocking. The proposed Capacity Exchange Protocol (CXP) is simpler than other proposed solutions for sharing resources in open real-time systems since it does not attempt to return the inherited capacity in the same exact amount to blocked servers. This loss of optimality is worth the reduced complexity as the protocol’s behaviour nevertheless tends to be fair and outperforms the previous solutions in highly dynamic scenarios as demonstrated by extensive simulations. A formal analysis of CXP is presented and the conditions under which it is possible to guarantee hard real-time tasks are discussed.

The quest for a balanced manpower capacity: different flexibility strategies examined

To cope with permanent fluctuations in demand, organizations are challenged to organize their manpower capacity in a flexible way. Different strategies of manpower planning are being used for this purpose. Using data from the 2002 Panel Survey of Organisations Flanders, we first verify to what extent temporal, contractual and functional flexibility strategies are applied in Flemish organizations. Subsequently, logistic regression is used to analyse the link between these flexible work strategies and a ‘fitting manpower capacity’. While the results show a negative association between the use of temporal or contractual flexibility measures and a balanced manpower capacity, functional flexibility seems to be positively related. The different logics in which numerical and functional flexibility proceed can be labeled as ‘curative’ versus ‘preventive’ strategies of flexibility. Further analyses discern between various interpretations of functional flexibility and assess whether different team types make a contribution to a fitting manpower capacity.

Shared resources and precedence constraints with capacity sharing and stealing

This paper proposes a new strategy to integrate shared resources and precedence constraints among real-time tasks, assuming no precise information on critical sections and computation times is available. The concept of bandwidth inheritance is combined with a greedy capacity sharing and stealing policy to efficiently exchange bandwidth among tasks, minimising the degree of deviation from the ideal system's behaviour caused by inter-application blocking. The proposed capacity exchange protocol (CXP) focus on exchanging extra capacities as early, and not necessarily as fairly, as possible. This loss of optimality is worth the reduced complexity as the protocol's behaviour nevertheless tends to be fair in the long run and outperforms other solutions in highly dynamic scenarios, as demonstrated by extensive simulations.

Does 6-minutes walk test predict functional capacity in elderly people?

Portugal has an accentuated aging tendency, presenting an elderly population (individuals with more than 65 years old) of 19.2%. The average life expectancy is 79.2 years. Thus, it’s important to maintain autonomy and independency as long as possible. Functional ability concept rises from the need to evaluate the capacity to conduct daily activities in an independent way. It can be estimated with the 6-minute walk test (6MWT) and other validated test. This test is simple, reliable, valid and consists in a daily activity (walk). The goals of this study was to verify associations between functional capacity measured with two different instruments (6MWT and Composite Physical Function (CPF) scale) and between those results and characterization variables.

Synthesis, characterization and reactivity of new cobalt, palladium and nickel complexes bearing α-diimines and P, O ligands

This work describes the synthesis and characterization of a series of new α-diimine and P,O, β-keto and acetamide phosphines ligands, and their complexation to Ni(II), Co(II),Co(III) and Pd(II) to obtain a series of new compounds aiming to study their structural characteristics and to test their catalytic activity. All the compounds synthesized were characterized by the usual spectroscopic and spectrometric techniques: Elemental Analysis, MALDI-TOF-MS spectrometry, IR, UV-vis, 1H, 13C and 31P NMR spectroscopies. Some of the paramagnetic compounds were also characterized by EPR. For the majority of the compounds it was possible to solve their solid state structure by single crystal X-ray diffraction. Tests for olefin polymerization were performed in order to determine the catalytic activity of the Co(II) complexes. Chapter I presents a brief introduction to homogenous catalysis, highlighting the reactions catalyzed by the type of compounds described in this thesis, namely olefin polymerization and oligomerization and reactions catalyzed by the complexes bearing α-diimines and P,O type ligands. Chapter II is dedicated to the description of the synthesis of new α-diimines cobalt (II) complexes, of general formula [CoX2(α-diimine)], where X = Cl or I and the α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl-1,4-diaza-1,3-butadiene (Ar-DAB). Structures solved by single crystal X-ray diffraction were obtained for all the described complexes. For some of the compounds, X-band EPR measurements were performed on polycrystalline samples, showing a high-spin Co(II) (S = 3/2) ion, in a distorted axial environment. EPR single crystal experiments on two of the compounds allowed us to determine the g tensor orientation in the molecular structure. In Chapter III we continue with the synthesis and characterization of more cobalt (II)complexes bearing α-diimines of general formula [CoX2(α-diimine)], with X = Cl or I and α-diimines are bis(aryl)acenaphthenequinonediimine) (Ar-BIAN) and 1,4-diaryl-2,3-dimethyl- 1,4-diaza-1,3-butadiene (Ar-DAB). The structures of three of the new compounds synthesized were determined by single crystal X-ray diffraction. A NMR paramagnetic characterization of all the compounds described is presented. Ethylene polymerization tests were done to determine the catalytic activity of several of the Co(II) complexes described in Chapter II and III and their results are shown. In Chapter IV a new rigid bidentate ligand, bis(1-naphthylimino)acenaphthene, and its complexes with Zn(II) and Pd(II), were synthesized. Both the ligand and its complexes show syn and anti isomers. Structures of the ligand and the anti isomer of the Pd(II) complex were solved by single crystal X-ray diffraction. All the compounds were characterized by elemental analysis, MALDI-TOF-MS spectrometry, and by IR, UV-vis, 1H, 13C, 1H-1H COSY, 1H-13C HSQC, 1H-13C HSQC-TOCSY and 1H-1H NOESY NMR when necessary. DFT studies showed that both conformers of [PdCl2(BIAN)] are isoenergetics and can be obtain experimentally. However, we can predict that the isomerization process is not available in square-planar complex, but is possible for the free ligand. The molecular geometry is very similar in both isomers, and only different orientations for naphthyl groups can be expected. Chapter V describes the synthesis of new P, O type ligands, β-keto phosphine, R2PCH2C(O)Ph, and acetamide phosphine R2PNHC(O)Me, as well as a series of new cobalt(III) complexes namely [(η5-C5H5)CoI2{Ph2PCH2C(O)Ph}], and [(η5- C5H5)CoI2{Ph2PNHC(O)Me}]. Treating these Co(III) compounds with an excess of Et3N, resulted in complexes η2-phosphinoenolate [(η5-C5H5)CoI{Ph2PCH…C(…O)Ph}] and η2- acetamide phosphine [(η5-C5H5)CoI{Ph2PN…C(…O)Me}]. Nickel (II) complexes were also obtained: cis-[Ni(Ph2PN…C(…O)Me)2] and cis-[Ni((i-Pr)2PN…C(…O)Me)2]. Their geometry and isomerism were discussed. Seven structures of the compounds described in this chapter were determined by single crystal X-ray diffraction. The general conclusions of this work can be found in Chapter VI.

Drilling of fibre reinforced plastic laminates

The use of fibre reinforced plastics – FRP’s – in structures is under a considerable increase. Advantages of their use are related with their low weight, high strength and stiffness. The improvement of the dynamic characteristics has been profitable for aeronautics, automobile, railway, naval and sporting goods industries. Drilling is a widely used machining technique as it is needed to assemble parts in a structure. This is a unique machining process, characterized by the existence of two different mechanisms: extrusion by the drill chisel edge and cutting by the rotating cutting lips. Drilling raises particular problems that can reduce mechanical and fatigue strength of the parts. In this work, quasi-isotropic hybrid laminates with 25% of carbon fibre reinforced plies and 4 mm thickness are produced, tested and drilled. Three different drill geometries are compared. Results considered are the interlaminar fracture toughness in Mode I – GIc –, thrust force during drilling and delamination extent after drilling. A bearing test is performed to evaluate tool influence on the load carrying capacity of the plate. Results consider the influence of drill geometry on delamination. A correlation linking plate damage to bearing test results is presented.

A sensor classification strategy for robotic manipulators

In practice the robotic manipulators present some degree of unwanted vibrations. The advent of lightweight arm manipulators, mainly in the aerospace industry, where weight is an important issue, leads to the problem of intense vibrations. On the other hand, robots interacting with the environment often generate impacts that propagate through the mechanical structure and produce also vibrations. In order to analyze these phenomena a robot signal acquisition system was developed. The manipulator motion produces vibrations, either from the structural modes or from endeffector impacts. The instrumentation system acquires signals from several sensors that capture the joint positions, mass accelerations, forces and moments, and electrical currents in the motors. Afterwards, an analysis package, running off-line, reads the data recorded by the acquisition system and extracts the signal characteristics. Due to the multiplicity of sensors, the data obtained can be redundant because the same type of information may be seen by two or more sensors. Because of the price of the sensors, this aspect can be considered in order to reduce the cost of the system. On the other hand, the placement of the sensors is an important issue in order to obtain the suitable signals of the vibration phenomenon. Moreover, the study of these issues can help in the design optimization of the acquisition system. In this line of thought a sensor classification scheme is presented. Several authors have addressed the subject of the sensor classification scheme. White (White, 1987) presents a flexible and comprehensive categorizing scheme that is useful for describing and comparing sensors. The author organizes the sensors according to several aspects: measurands, technological aspects, detection means, conversion phenomena, sensor materials and fields of application. Michahelles and Schiele (Michahelles & Schiele, 2003) systematize the use of sensor technology. They identified several dimensions of sensing that represent the sensing goals for physical interaction. A conceptual framework is introduced that allows categorizing existing sensors and evaluates their utility in various applications. This framework not only guides application designers for choosing meaningful sensor subsets, but also can inspire new systems and leads to the evaluation of existing applications. Today’s technology offers a wide variety of sensors. In order to use all the data from the diversity of sensors a framework of integration is needed. Sensor fusion, fuzzy logic, and neural networks are often mentioned when dealing with problem of combing information from several sensors to get a more general picture of a given situation. The study of data fusion has been receiving considerable attention (Esteban et al., 2005; Luo & Kay, 1990). A survey of the state of the art in sensor fusion for robotics can be found in (Hackett & Shah, 1990). Henderson and Shilcrat (Henderson & Shilcrat, 1984) introduced the concept of logic sensor that defines an abstract specification of the sensors to integrate in a multisensor system. The recent developments of micro electro mechanical sensors (MEMS) with unwired communication capabilities allow a sensor network with interesting capacity. This technology was applied in several applications (Arampatzis & Manesis, 2005), including robotics. Cheekiralla and Engels (Cheekiralla & Engels, 2005) propose a classification of the unwired sensor networks according to its functionalities and properties. This paper presents a development of a sensor classification scheme based on the frequency spectrum of the signals and on a statistical metrics. Bearing these ideas in mind, this paper is organized as follows. Section 2 describes briefly the robotic system enhanced with the instrumentation setup. Section 3 presents the experimental results. Finally, section 4 draws the main conclusions and points out future work.

Insights into the mechanims underlyng the antiproliferative potential of a Co(II) coordination compound bearing 1,10-Phenanthroline-5,6-Dione: DNA and protein interaction studies

The very high antiproliferative activity of [Co(Cl)(H2O)(phendione)(2)][BF4] (phendione is 1,10-phenanthroline-5,6-dione) against three human tumor cell lines (half-maximal inhibitory concentration below 1 mu M) and its slight selectivity for the colorectal tumor cell line compared with healthy human fibroblasts led us to explore the mechanisms of action underlying this promising antitumor potential. As previously shown by our group, this complex induces cell cycle arrest in S phase and subsequent cell death by apoptosis and it also reduces the expression of proteins typically upregulated in tumors. In the present work, we demonstrate that [Co(Cl)(phendione)(2)(H2O)][BF4] (1) does not reduce the viability of nontumorigenic breast epithelial cells by more than 85 % at 1 mu M, (2) promotes the upregulation of proapoptotic Bax and cell-cycle-related p21, and (3) induces release of lactate dehydrogenase, which is partially reversed by ursodeoxycholic acid. DNA interaction studies were performed to uncover the genotoxicity of the complex and demonstrate that even though it displays K (b) (+/- A standard error of the mean) of (3.48 +/- A 0.03) x 10(5) M-1 and is able to produce double-strand breaks in a concentration-dependent manner, it does not exert any clastogenic effect ex vivo, ruling out DNA as a major cellular target for the complex. Steady-state and time-resolved fluorescence spectroscopy studies are indicative of a strong and specific interaction of the complex with human serum albumin, involving one binding site, at a distance of approximately 1.5 nm for the Trp214 indole side chain with log K (b) similar to 4.7, thus suggesting that this complex can be efficiently transported by albumin in the blood plasma.