Resolution of isomeric multi-ruthenated porphyrins by travelling wave ion mobility mass spectrometry

The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (Rp-p). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N-2 and CO2 were tested as the drift gas, and similar a but considerably better values of R-p and Rp-p were always observed for CO2. Copyright (C) 2012 John Wiley & Sons, Ltd.

The education of the body for an "integral soldier", "physically strong, intelligent and soul superior"

This study examines the paramilitary training carried out by the Integralist Militia (Militia Integralista), unit of the Brazilian Integralist Action (Acao Integralista Brasileira, AIB) of the extreme right wing political party in Brazil in the 1930s. The training was aimed to create the "integral soldier", a "physically strong, intelligent and soul superior" one. The study analyzes issues of the newspaper "Monitor Integralista", a prescriptive and dogmatic journal of the movement, found in the Public and History Archives of the city of Rio Claro, State of Sao Paulo, and in the "A Offensiva" newspaper, microfilmed an archived at the National Library of Rio de Janeiro. It concludes that Plinio Salgado's goal, the National Head of the AIB, was to train, by using verbal persuasion, speeches, word of mouth and by vote, by force and physical combat, the integralists to defend the causes of the movement.

New approach for power transformer protection based on intelligent hybrid systems

A power transformer needs continuous monitoring and fast protection as it is a very expensive piece of equipment and an essential element in an electrical power system. The most common protection technique used is the percentage differential logic, which provides discrimination between an internal fault and different operating conditions. Unfortunately, there are some operating conditions of power transformers that can mislead the conventional protection affecting the power system stability negatively. This study proposes the development of a new algorithm to improve the protection performance by using fuzzy logic, artificial neural networks and genetic algorithms. An electrical power system was modelled using Alternative Transients Program software to obtain the operational conditions and fault situations needed to test the algorithm developed, as well as a commercial differential relay. Results show improved reliability, as well as a fast response of the proposed technique when compared with conventional ones.

Quantitative comparison of mobility and gross motor function in Brazilian children with cerebral palsy

Background: Cerebral palsy (CP) presents changes in posture and movement as a core characteristic, which requires therapeutic monitoring during the habilitation or rehabilitation of children. Besides clinical treatment, it is fundamental that professionals use systems of evaluation to quantify the difficulties presented to the individual and assist in the organization of a therapeutic program. The aim of this study was to quantitatively verify the performance of children with spastic di-paresia type CP. Methods: The Pediatric Evaluation of Disability Inventory (PEDI) and Gross Motor Function Classification System (GMFM) tests were used and classification made through the GMFCS in the assessment of 7 patients with CP, 4 females and 3 males, average age of 9 years old. Results: According to GMFCS scales, 17% (n=1) were level II and 83% (n=6) were level III. The PEDI test and 88 GMFM items were used in the area of mobility. We observed that there was high correlation between mobility and gross motor function with Pearson's correlation coefficient =0.929) showing the likely impact of these areas in the functional skills and the quality of life of these patients. Conclusion: We suggest the impact of the limitation of the areas in functional skills and quality of life of these patients.

Modeling of active holonic control systems for intelligent buildings

Building facilities have become important infrastructures for modern productive plants dedicated to services. In this context, the control systems of intelligent buildings have evolved while their reliability has evidently improved. However, the occurrence of faults is inevitable in systems conceived, constructed and operated by humans. Thus, a practical alternative approach is found to be very useful to reduce the consequences of faults. Yet, only few publications address intelligent building modeling processes that take into consideration the occurrence of faults and how to manage their consequences. In the light of the foregoing, a procedure is proposed for the modeling of intelligent building control systems, considersing their functional specifications in normal operation and in the of the event of faults. The proposed procedure adopts the concepts of discrete event systems and holons, and explores Petri nets and their extensions so as to represent the structure and operation of control systems for intelligent buildings under normal and abnormal situations. (C) 2012 Elsevier B.V. All rights reserved.

Determination of carrier mobility in MEH-PPV thin-films by stationary and transient current techniques

Charge transport and shelf-degradation of MEH-PPV thin-films were investigated through stationary (e.g. current versus voltage - JxV) and transient (e.g. Time-of-Flight - ToF, Dark-Injection Space-Charge-Limited Current - DI-SCLC, Charge Extraction by Linearly Increasing Voltage - CELN) current techniques. Charge carrier mobility in nanometric films was best characterized through JxV and DI-SCLC. It approaches 10(-6) cm(2)Ns under a SCLC regime with deep traps for light-emitting diode applications. ToF measurements performed on micrometric layers (i.e. - 3 mu m) confirmed studies in 100 nm-thick films as deposited in OLEDs. All results were comparable to a similar poly(para-phenylene vinylene) derivative, MDMO-PPV. Electrical properties extracted from thin-film transistors demonstrated mobility dependence on carrier concentration in the channel (similar to 10(-7)-10(-4) cm(2)/Vs). At low accumulated charge levels and reduced free carrier concentration, a perfect agreement to the previously cited techniques was observed. Degradation was verified through mobility reduction and changes in trap distribution of states. (C) 2011 Elsevier B.V. All rights reserved.

Corrole isomers: intrinsic gas-phase shapes via traveling wave ion mobility mass spectrometry and dissociation chemistries via tandem mass spectrometry

Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most "confused" isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH3, allowing its prompt differentiation from the other isomers.

Benchmarking sustainable urban mobility: The case of Curitiba, Brazil

Transportation planning is currently being confronted with a broader planning view, which is given by the concept of mobility. The Index of Sustainable Urban Mobility (I_SUM) is among the tools developed for supporting this new concept implementation. It is a tool to assess the current mobility conditions of any city, which can also be applied for policy formulation. This study focus on the application of I_SUM in the city of Curitiba, Brazil. Considering that the city is known worldwide as a reference of successful urban and transportation planning, the index application must confirm it. An additional objective of the study was to evaluate the index itself, or the subjacent assessment method and reference values. A global I_SUM value of 0.747 confirmed that the city has indeed very positive characteristics regarding sustainable mobility policies. However, some deficiencies were also detected, particularly with respect to non-motorized transport modes. The application has also served to show that a few I_SUM indicators were not able to capture some of the positive aspects of the city, what may suggest the need of changes in their formulation. Finally, the index application in parts of the city suggests that the city provides fair and equitable mobility conditions to all citizens throughout the city. This is certainly a good attribute for becoming a benchmark of sustainable mobility, even if it is not yet the ideal model. (C) 2012 Elsevier Ltd. All rights reserved.

Exploring the coordination chemistry of isomerizable terpyridine derivatives for successful analyses of cis and trans isomers by travelling wave ion mobility mass spectrometry

The photochemical cis-trans isomerization of the 4-{4-[2-(pyridin-4-yl)ethenyl]phenyl}-2,2': 6',2''-terpyridine ligand (vpytpy) was investigated by UV-vis, NMR and TWIM-MS. Ion mobility mass spectrometry was performed pursuing the quantification of the isomeric composition during photolysis, however an in-source trans-to-cis isomerization process was observed. In order to overcome this inherent phenomenon, the isomerization of the vpytpy species was suppressed by complexation, reacting with iron(II) ions, and forming the [Fe(vpytpy)(2)](2+) complex. The strategy of "freezing" the cis-trans isomerizable ligand at a given geometric conformation was effective, preventing further isomerization, thus allowing the distinction of each one of the isomers in the photolysed mixture. In addition, the experimental drift times were related to the calculated surface areas of the three possible cis-cis, cis-trans and trans-trans iron(II) complex isomers. The stabilization of the ligand in a given conformation also allows us to obtain the cis-cis and cis-trans complexes exhibiting the ligand in the metastable cis-conformation, as well as in the thermodynamically stable trans-conformation.

Protomers: formation, separation and characterization via travelling wave ion mobility mass spectrometry

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH3, whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO2 loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups. Copyright (C) 2012 John Wiley & Sons, Ltd.

Intelligent tutoring system for distance education

This study aims to develop and implement a tool called intelligent tutoring system in an online course to help a formative evaluation in order to improve student learning. According to Bloom et al. (1971,117) formative evaluation is a systematic evaluation to improve the process of teaching and learning. The intelligent tutoring system may provide a timely and high quality feedback that not only informs the correctness of the solution to the problem, but also informs students about the accuracy of the response relative to their current knowledge about the solution. Constructive and supportive feedback should be given to students to reveal the right and wrong answers immediately after taking the test. Feedback about the right answers is a form to reinforce positive behaviors. Identifying possible errors and relating them to the instructional material may help student to strengthen the content under consideration. The remedial suggestion should be given in each answer with detaileddescription with regards the materials and instructional procedures before taking next step. The main idea is to inform students about what they have learned and what they still have to learn. The open-source LMS called Moodle was extended to accomplish the formative evaluation, high-quality feedback, and the communal knowledge presented here with a short online financial math course that is being offered at a large University in Brazil. The preliminary results shows that the intelligent tutoring system using high quality feedback helped students to improve their knowledge about the solution to the problems based on the errors of their past cohorts. The results and suggestion for future work are presented and discussed.

Recent trends in intelligent data analysis

European Regional Development Fund

Order induced charge carrier mobility enhancement in columnar liquid crystal diodes

Discotic molecules comprising a rigid aromatic core and flexible side chains have been promisingly applied in OLEDs as self-organizing organic semiconductors. Due to their potentially high charge carrier mobility along the columns, device performance can be readily improved by proper alignment of columns throughout the bulk. In the present work, the charge mobility was increased by 5 orders of magnitude due to homeotropic columnar ordering induced by the boundary interfaces during thermal annealing in the mesophase. State-of-the-art diodes were fabricated using spin-coated films whose homeotropic alignment with formation of hexagonal germs was observed by polarizing optical microscopy. The photophysical properties showed drastic changes at the mesophase-isotropic transition, which is supported by the gain of order observed by X-ray diffraction. The electrical properties were investigated by modeling the current−voltage characteristics by a space-charge-limited current transport with a field dependent mobility.