Energy Transfer in Nanostructured Films Containing Poly(p-phenylene vinylene) and Acceptor Species

The combination of luminescent polymers and suitable energy-accepting materials may lead to a molecular-level control of luminescence in nanostructured films. In this study, the properties of layer-by-layer (LbL) films of polyp-phenylene vinylene) (PPV) were investigated with steady-state and time-resolved fluorescence spectroscopies, where fluorescence quenching was controlled by interposing inert polyelectrolyte layers between the PPV donor and acceptor layers made with either Congo Red (CR) or nickel tetrasulfonated phthalocyanine (NiTsPc). The dynamics of the excited state of PPV was affected by the energy-accepting layers, thus confirming the presence of resonant energy transfer mechanisms. Owing to the layered structured of both energy donor and acceptor units, energy transfer varied with the distance between layers, r, according to 1/r(n) with n = 2 or 3, rather than with 1/r(6) predicted by the Forster theory for interacting point dipoles.

Quasi-perfect state transfer in a bosonic dissipative network

In this paper we propose a scheme for quasi-perfect state transfer in a network of dissipative harmonic oscillators. We consider ideal sender and receiver oscillators connected by a chain of nonideal transmitter oscillators coupled by nearest-neighbour resonances. From the algebraic properties of the dynamical quantities describing the evolution of the network state, we derive a criterion, fixing the coupling strengths between all the oscillators, apart from their natural frequencies, enabling perfect state transfer in the particular case of ideal transmitter oscillators. Our criterion provides an easily manipulated formula enabling perfect state transfer in the special case where the network nonidealities are disregarded. We also extend such a criterion to dissipative networks where the fidelity of the transferred state decreases due to the loss mechanisms. To circumvent almost completely the adverse effect of decoherence, we propose a protocol to achieve quasi-perfect state transfer in nonideal networks. By adjusting the common frequency of the sender and the receiver oscillators to be out of resonance with that of the transmitters, we demonstrate that the sender`s state tunnels to the receiver oscillator by virtually exciting the nonideal transmitter chain. This virtual process makes negligible the decay rate associated with the transmitter line at the expense of delaying the time interval for the state transfer process. Apart from our analytical results, numerical computations are presented to illustrate our protocol.

Spectrofluorimetric Determination of Second Critical Micellar Concentration of SDS and SDS/Brij 30 Systems

Potentially useful stead-state fluorimetric technique was used to determine the critical micellar concentrations (CMC(1) and CMC(2)) for two micellar media, one formed by SDS and the other by SDS/Brij 30. A comparative study based on conductimetric and surfacial tension measurements suggests that the CMC(1) estimated by the fluorimetric method is lower than the value estimated by these other techniques. Equivalent values were observed for SDS micelles without Brij 30 neutral co-surfactant. The use of acridine orange as fluorescent probe permitted to determine both CMC(1) and CMC(2). Based on it an explanation on aspects of micelle formation mechanism is presented, particularly based on a spherical and a rod like structures.

The intramolecular charge transfer in a donor-pi-acceptor dianion probed by resonance Raman spectroscopy and quantum chemical calculations

The dideprotonation of 4-(4-nitrophenylazo)resorcinol generates an anionic species with substantial electronic pi delocalization. As compared to the parent neutral species, the anionic first excited electronic transition, characterized as an intramolecular charge transfer (ICT) from the CO(-) groups to the NO(2) moiety, shows a drastic red shift of ca. 200 nm in the lambda(max) in the UV-vis spectrum, leading to one of the lowest ICT energies observed (lambda(max) = 630 nm in dimethyl sulfoxide (DMSO)) in this class of push-pull molecular systems. Concomitantly, a threefold increase in the molar absorptivity (epsilon(max)) in comparison to the neutral species is observed. The resonance Raman enhancement profiles reveal that in the neutral species the chromophore involves several modes, as nu(C-N), nu(N=N), nu(C=C) and nu(s)(NO(2)), whereas in the dianion, there is a selective enhancement of the NO(2) vibrational modes. The quantum chemical calculations of the electronic transitions and vibrational wavenumbers led to a consistent analysis of the enhancement patterns observed in the resonance Raman spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

Catalytic oxidation of hydrocarbons by trinuclear mu-oxo-bridged ruthenium-acetate clusters: Radical versus non-radical mechanisms

The [Ru(3)O(H(3)CCO(2))(6)(py)(2)(L)]PF(6) clusters, where L=methanol or dimethyl sulfoxide, can be activated by peroxide or oxygen donor species, such as tert-butyl hydroperoxide (TBHP) or iodosylbenzene (PhIO), respectively, generating reactive intermediates of the type [Ru(3)(IV,IV,III)=0](+). In this way, they catalyse the oxidation of cyclohexane or cyclohexene by TBHP and PhIO, via oxygen atom transfer, rather than by the alternative oxygen radical mechanism characteristic of this type of complexes. In addition to their ability to perform efficient olefin epoxydation catalysis, these clusters also promote the cleavage of the C-H bond in hydrocarbons, resembling the oxidation catalysis by metal porphyrins. (C) 2008 Elsevier Inc. All rights reserved.

Quenching of Photoactivity in Phthalocyanine Copper(II)-Titanate Nanotube Hybrid Systems

Titanate nanotubes (TiNTs) were obtained by hydrothermal treatment of anatase powder in aqueous NaOH solution and then modified with 2,9,16,23-tertracarboxyl phthalocyanine copper(H) (CuPc). This hybrid organic inorganic nanoscopic system was characterized by X-ray diffraction, microscopy, and spectroscopy. Transmission electron microscopy (TEM) images of pure and modified TiNTs revealed multiwall structures with an average outer diameter of 9 nm and a length of several hundred nanometers. The tubular morphology of the TiNTs was covered with CuPc-film. The amount of CuPc adsorbed onto the TiNTs was quantified by electron paramagnetic resonance (EPR). Using the same technique and spin-trapping methodology, the photogeneration of reactive oxygen species (ROS) from the TiNTs was systematically investigated. A drastic quenching of photoactivity was observed in the CuPc/TiNT hybrid system. Electron transfer from excited CuPc states to the TiNT conduction band followed by electron recombination may be the cause of this quenching.

Gas-Phase Acylium Ion Transfer Reactions Mediated by a Proton Shuttle Mechanism

The mechanism and the energy profile of the gas-phase reaction that mimics esterification under acidic conditions have been investigated at different levels of theory. These reactions are known to proceed with rate constants close to the collision limit in the gas-phase and questions have been raised as to whether the typical addition-elimination mechanism via a tetrahedral intermediate can explain the ease of these processes. Because these reactions are common to many organic and biochemical processes it is important to understand the intrinsic reactivity of these systems. Our calculations at different levels of theory reveal that a stepwise mechanism via a tetrahedral species is characterized by energy barriers that are inconsistent with the experimental results. For the thermoneutral exchange between protonated acetic acid and water and the exothermic reaction of protonated acetic acid and methanol our calculations show that these reactions proceed initially by a proton shuttle between the carbonyl oxygen and the hydroxy oxygen of acetic acid mediated by water, or methanol, followed by displacement at the acylium ion center. These findings suggest that the reactions in the gas-phase should be viewed as an acylium ion transfer reaction. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1596-1606, 2011

Using locally available components and local knowledge to build sustainable stand-alone power systems

The aim of this paper is to point out benefits as well as disadvantages associated with the use of locally available, not necessarily standardized, components in stand-alone electrical power systems at rural locations. Advantages and challenges arising when the direct involvement in design, construction and maintenance of the power system is reserved to people based in the area of implementation are discussed. The presented research is centered around one particular PV-diesel hybrid system in Tanzania; a case study in which technical and social aspects related to the particular power system are studied.

Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.

A Framework supporting collaboration on the distributed design of integrated systems

The work described in this thesis aims to support the distributed design of integrated systems and considers specifically the need for collaborative interaction among designers. Particular emphasis was given to issues which were only marginally considered in previous approaches, such as the abstraction of the distribution of design automation resources over the network, the possibility of both synchronous and asynchronous interaction among designers and the support for extensible design data models. Such issues demand a rather complex software infrastructure, as possible solutions must encompass a wide range of software modules: from user interfaces to middleware to databases. To build such structure, several engineering techniques were employed and some original solutions were devised. The core of the proposed solution is based in the joint application of two homonymic technologies: CAD Frameworks and object-oriented frameworks. The former concept was coined in the late 80's within the electronic design automation community and comprehends a layered software environment which aims to support CAD tool developers, CAD administrators/integrators and designers. The latter, developed during the last decade by the software engineering community, is a software architecture model to build extensible and reusable object-oriented software subsystems. In this work, we proposed to create an object-oriented framework which includes extensible sets of design data primitives and design tool building blocks. Such object-oriented framework is included within a CAD Framework, where it plays important roles on typical CAD Framework services such as design data representation and management, versioning, user interfaces, design management and tool integration. The implemented CAD Framework - named Cave2 - followed the classical layered architecture presented by Barnes, Harrison, Newton and Spickelmier, but the possibilities granted by the use of the object-oriented framework foundations allowed a series of improvements which were not available in previous approaches: - object-oriented frameworks are extensible by design, thus this should be also true regarding the implemented sets of design data primitives and design tool building blocks. This means that both the design representation model and the software modules dealing with it can be upgraded or adapted to a particular design methodology, and that such extensions and adaptations will still inherit the architectural and functional aspects implemented in the object-oriented framework foundation; - the design semantics and the design visualization are both part of the object-oriented framework, but in clearly separated models. This allows for different visualization strategies for a given design data set, which gives collaborating parties the flexibility to choose individual visualization settings; - the control of the consistency between semantics and visualization - a particularly important issue in a design environment with multiple views of a single design - is also included in the foundations of the object-oriented framework. Such mechanism is generic enough to be also used by further extensions of the design data model, as it is based on the inversion of control between view and semantics. The view receives the user input and propagates such event to the semantic model, which evaluates if a state change is possible. If positive, it triggers the change of state of both semantics and view. Our approach took advantage of such inversion of control and included an layer between semantics and view to take into account the possibility of multi-view consistency; - to optimize the consistency control mechanism between views and semantics, we propose an event-based approach that captures each discrete interaction of a designer with his/her respective design views. The information about each interaction is encapsulated inside an event object, which may be propagated to the design semantics - and thus to other possible views - according to the consistency policy which is being used. Furthermore, the use of event pools allows for a late synchronization between view and semantics in case of unavailability of a network connection between them; - the use of proxy objects raised significantly the abstraction of the integration of design automation resources, as either remote or local tools and services are accessed through method calls in a local object. The connection to remote tools and services using a look-up protocol also abstracted completely the network location of such resources, allowing for resource addition and removal during runtime; - the implemented CAD Framework is completely based on Java technology, so it relies on the Java Virtual Machine as the layer which grants the independence between the CAD Framework and the operating system. All such improvements contributed to a higher abstraction on the distribution of design automation resources and also introduced a new paradigm for the remote interaction between designers. The resulting CAD Framework is able to support fine-grained collaboration based on events, so every single design update performed by a designer can be propagated to the rest of the design team regardless of their location in the distributed environment. This can increase the group awareness and allow a richer transfer of experiences among them, improving significantly the collaboration potential when compared to previously proposed file-based or record-based approaches. Three different case studies were conducted to validate the proposed approach, each one focusing one a subset of the contributions of this thesis. The first one uses the proxy-based resource distribution architecture to implement a prototyping platform using reconfigurable hardware modules. The second one extends the foundations of the implemented object-oriented framework to support interface-based design. Such extensions - design representation primitives and tool blocks - are used to implement a design entry tool named IBlaDe, which allows the collaborative creation of functional and structural models of integrated systems. The third case study regards the possibility of integration of multimedia metadata to the design data model. Such possibility is explored in the frame of an online educational and training platform.

Understanding e-government technology transfer: evidence from the transfer of a patent management system from EPO to INPI

Drawing upon Brazilian experience, this research explores some of the key issues to be addressed in using e-government technical cooperation designed to enhance service provision of Patent Offices in developing countries. While the development of software applications is often seen merely as a technical engineering exercise, localization and adaptation are context bounded matters that are characterized by many entanglements of human and non-humans. In this work, technical, legal and policy implications of technical cooperation are also discussed in a complex and dynamic implementation environment characterized by the influence of powerful hidden agendas associated with the arena of intellectual property (IP), which are shaped by recent technological, economic and social developments in our current knowledge-based economy. This research employs two different theoretical lenses to examine the same case, which consists of transfer of a Patent Management System (PMS) from the European Patent Office (EPO) to the Brazilian Patent Office that is locally named ‘Instituto Nacional da Propriedade Industrial’ (INPI). Fundamentally, we have opted for a multi-paper thesis comprising an introduction, three scientific articles and a concluding chapter that discusses and compares the insights obtained from each article. The first article is dedicated to present an extensive literature review on e-government and technology transfer. This review allowed the proposition on an integrative meta-model of e-government technology transfer, which is named E-government Transfer Model (ETM). Subsequently, in the second article, we present Actor-Network Theory (ANT) as a framework for understanding the processes of transferring e-government technologies from Patent Offices in developed countries to Patent Offices in developing countries. Overall, ANT is seen as having a potentially wide area of application and being a promising theoretical vehicle in IS research to carry out a social analysis of messy and heterogeneous processes that drive technical change. Drawing particularly on the works of Bruno Latour, Michel Callon and John Law, this work applies this theory to a longitudinal study of the management information systems supporting the Brazilian Patent Office restructuration plan that involved the implementation of a European Patent Management System in Brazil. Based upon the ANT elements, we follow the actors to identify and understand patterns of group formation associated with the technical cooperation between the Brazilian Patent Office (INPI) and the European Patent Office (EPO). Therefore, this research explores the intricate relationships and interactions between human and non-human actors in their attempts to construct various network alliances, thereby demonstrating that technologies embodies compromise. Finally, the third article applies ETM model as a heuristic frame to examine the same case previously studied from an ANT perspective. We have found evidence that ETM has strong heuristic qualities that can guide practitioners who are engaged in the transfer of e-government systems from developed to developing countries. The successful implementation of e-government projects in developing countries is important to stimulate economic growth and, as a result, we need to understand the processes through which such projects are being implemented and succeed. Here, we attempt to improve understanding on the development and stabilization of a complex social-technical system in the arena of intellectual property. Our preliminary findings suggest that e-government technology transfer is an inherently political process and that successful outcomes require continuous incremental actions and improvisations to address the ongoing issues as they emerge.

New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.

The co-catalytic effect of chlorpromazine on peroxidase-mediated oxidation of melatonin: enhanced production of N-1-acetyl-N (2)-formyl-5-methoxykynuramine

Accumulating evidence points to relationships between increased production of reactive oxygen or decreased antioxidant protection in schizophrenic patients. Chlorpromazine (CPZ), which remains a benchmark treatment for people with schizophrenia, has been described as a pro-oxidant compound. Because the antioxidant compound melatonin exerts protective effects against CPZ-induced liver disease in rats, in this investigation, our main objective was to study the effect of CPZ as a co-catalyst of peroxidase-mediated oxidation of melatonin. We found that melatonin was an excellent reductor agent of preformed CPZ cation radical (CPZ(center dot+)). The addition of CPZ during the horseradish peroxidase (HRP)-catalyzed oxidation of melatonin provoked a significant increase in the rate of oxidation and production of N-1-acetyl-N-2-formyl-5-methoxykynuramine (AFMK). Similar results were obtained using myeloperoxidase. The effect of CPZ on melatonin oxidation was rather higher at alkaline pH. At pH 9.0, the efficiency of oxidation of melatonin was 15 times higher and the production of AFMK was 30 times higher as compared with the assays in the absence of CPZ. We suggest that CPZ is able to exacerbate the rate of oxidation of melatonin by an electron transfer mechanism where CPZ(center dot+), generated during the peroxidase-catalyzed oxidation, is able to efficiently oxidize melatonin.

Pole placement method using the system matrix transfer function and sparsity

This paper presents a pole placement method using both the augmented Jacobian and the corresponding system transfer function matrices. From the manipulation of these matrices a straightforward approach results to get the coefficients of a non-linear system, whose solution gives the parameters of the stabilizers that can provide a pre-specified minimum damping to the system. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Morphology and histology of male and female reproductive systems in the inseminating species Scoloplax distolothrix (Ostariophysi : Siluriformes : Scoloplacidae)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)