Donor-acceptor π−π stacking interactions: from small molecule complexes to healable supramolecular polymer networks

This chapter presents selected literature examples to review the development of the use of donor–acceptor π–π stacking interactions as transient cross-links in supramolecular polymer networks. The chapter examines notable examples of these highly specific and directional interactions and illustrates how they can be utilised to reliably produce functional supramolecular, self-assembled systems. Knowledge gained from these fundamental studies has enabled the design, synthesis and application of donor–acceptor stacked supramolecular motifs in non-covalent polymer networks, which is exemplified through detailing the production, physical properties and optimisation of healable materials.

Second-order model for remote and close-up short-circuit faults currents on DC traction supply

A technique to calculate the current waveform for both close-up and remote short-circuit faults on DC supplied railways and subways is presented. Exact DC short-circuit current calculation is best performed by sophisticated computer transient simulations. However, an accurate simplified calculation method based on second-order approximation which can be easily executed with the help of a calculator or a spreadsheet program is proposed.

Fully electrochemical hyphenated flow system for preconcentration, cleanup, stripping, capillary electrophoresis with stacking and contactless conductivity detection of trace heavy metals

Successful coupling of electrochemical preconcentration (EPC) to capillary electrophoresis (CE) with contactless conductivity detection (C(4)D) is reported for the first time. The EPC-CE interface comprises a dual glassy carbon electrode (GCE) block, a spacer and an upper block with flow inlet and outlet, pseudo-reference electrode and a fitting for the CE silica column, consisting of an orifice perpendicular to the surface of a glassy carbon electrode with a bushing inside to ensure a tight press fit. The end of the capillary in contact with the GCE is slant polished, thus defining a reproducible distance from the electrode surface to the column bore. First results with EPC-CE-C(4)D are very promising, as revealed by enrichment factors of two orders of magnitude for Tl, Cu, Pb and Cd ion peak area signals. Detection limits for 10 min deposition time fall around 20 nmol L(-1) with linear calibration curves over a wide range. Besides preconcentration, easy matrix exchange between accumulation and stripping/injection favors procedures like sample cleanup and optimization of pH, ionic strength and complexing power. This was demonstrated for highly saline samples by using a low conductivity buffer for stripping/injection to improve separation and promote field-enhanced sample stacking during electromigration along the capillary. (C) 2010 Elsevier B.V. All rights reserved.

Sample stacking in CZE using dynamic thermal junctions I. Analytes with low dpK(a)/dT crossing a single thermally induced pH junction in a BGE with high dpH/dT

The possibility to compress analyte bands at the beginning of CE runs has many advantages. Analytes at low concentration can be analyzed with high signal-to-noise ratios by using the so-called sample stacking methods. Moreover, sample injections with very narrow initial band widths (small initial standard deviations) are sometimes useful, especially if high resolutions among the bands are required in the shortest run time. In the present work, a method of sample stacking is proposed and demonstrated. It is based on BGEs with high thermal sensitive pHs (high dpH/dT) and analytes with low dpK(a)/dT. High thermal sensitivity means that the working pK(a) of the BGE has a high dpK(a)/dT in modulus. For instance, Tris and Ethanolamine have dpH/dT = -0.028/degrees C and -0.029/degrees C, respectively, whereas carboxylic acids have low dpK(a)/dT values, i.e. in the -0.002/degrees C to+0.002/degrees C range. The action of cooling and heating sections along the capillary during the runs affects also the local viscosity, conductivity, and electric field strength. The effect of these variables on electrophoretic velocity and band compression is theoretically calculated using a simple model. Finally, this stacking method was demonstrated for amino acids derivatized with naphthalene-2,3-dicarboxaldehyde and fluorescamine using a temperature difference of 70 degrees C between two neighbor sections and Tris as separation buffer. In this case, the BGE has a high pH thermal coefficient whereas the carboxylic groups of the analytes have low pK(a) thermal coefficients. The application of these dynamic thermal gradients increased peak height by a factor of two (and decreased the standard deviations of peaks by a factor of two) of aspartic acid and glutamic acid derivatized with naphthalene-2,3-dicarboxaldehyde and serine derivatized with fluorescamine. The effect of thermal compression of bands was not observed when runs were accomplished using phosphate buffer at pH 7 (negative control). Phosphate has a low dpH/dT in this pH range, similar to the dK(a)/dT of analytes. It is shown that vertical bar dK(a)/dT-dpH/dT vertical bar >> 0 is one determinant factor to have significant stacking produced by dynamic thermal junctions.

Sample stacking in CZE using dynamic thermal junctions II: Analytes with high dpK(a)/dT crossing a single thermal junction in a BGE with low dpH/dT

In a previous work [M. Mandaji, et al., this issue] a sample stacking method was theoretically modeled and experimentally demonstrated for analytes with low dpK(a)/dT (analytes carrying carboxylic groups) and BGEs with high dpH/dT (high pH-temperature-coefficients). In that work, buffer pH was modulated with temperature, inducing electrophoretic mobility changes in the analytes. In the present work, the opposite conditions are studied and tested, i.e. analytes with high dpK(a)/dT and BGEs that exhibit low dpH/dT. It is well known that organic bases such as amines, imidazoles, and benzimidazoles exhibit high dpK(a)/dT. Temperature variations induce instantaneous changes on the basicity of these and other basic groups. Therefore, the electrophoretic velocity of some analytes changes abruptly when temperature variations are applied along the capillary. This is true only if BGE pH remains constant or if it changes in the opposite direction of pK(a) of the analyte. The presence of hot and cold sections along the capillary also affects local viscosity, conductivity, and electric field strength. The effect of these variables on electrophoretic velocity and band stacking efficacy was also taken into account in the theoretical model presented. Finally, this stacking method is demonstrated for lysine partially derivatized with naphthalene-2,3-dicarboxaldehyde. In this case, the amino group of the lateral chain was left underivatized and only the alpha amino group was derivatized. Therefore, the basicity of the lateral amino group, and consequently the electrophoretic mobility, was modulated with temperature while the pH of the buffer used remained unchanged.

Aplicação de sistemas multi-classificadores no diagnóstico de falhas em motores de indução trifásicos

Equipment maintenance is the major cost factor in industrial plants, it is very important the development of fault predict techniques. Three-phase induction motors are key electrical equipments used in industrial applications mainly because presents low cost and large robustness, however, it isn t protected from other fault types such as shorted winding and broken bars. Several acquisition ways, processing and signal analysis are applied to improve its diagnosis. More efficient techniques use current sensors and its signature analysis. In this dissertation, starting of these sensors, it is to make signal analysis through Park s vector that provides a good visualization capability. Faults data acquisition is an arduous task; in this way, it is developed a methodology for data base construction. Park s transformer is applied into stationary reference for machine modeling of the machine s differential equations solution. Faults detection needs a detailed analysis of variables and its influences that becomes the diagnosis more complex. The tasks of pattern recognition allow that systems are automatically generated, based in patterns and data concepts, in the majority cases undetectable for specialists, helping decision tasks. Classifiers algorithms with diverse learning paradigms: k-Neighborhood, Neural Networks, Decision Trees and Naïves Bayes are used to patterns recognition of machines faults. Multi-classifier systems are used to improve classification errors. It inspected the algorithms homogeneous: Bagging and Boosting and heterogeneous: Vote, Stacking and Stacking C. Results present the effectiveness of constructed model to faults modeling, such as the possibility of using multi-classifiers algorithm on faults classification

Efeitos das técnicas breath-stacking e espirometria de incentivo nos volumes da caixa torácica em pacientes com Doença de Parkinson

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

A polaronic stacking fault defect model for CaCu3Ti4O12 material: an approach for the origin of the huge dielectric constant and semiconducting coexistent features

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Self-assembly of organometallic Pd(II) complexes via CH3 center dot center dot center dot pi interactions: the first example of a cyclopalladated compound with herringbone stacking pattern

Two binuclear cyclometallated compounds [Pd(C-2,N-dmba)(mu-N-3)](2) (1) and [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] (2) (dmba = N,N-dimethylbenzylarnine) have been synthesized and characterized by elemental 3 analysis, IR and NMR spectroscopies and single crystal X-ray diffraction crystallography. The ability of CH3 groups to form C(sp(3))-H...pi hydrogen bonds with phenyl rings is responsible for the molecular self-assembly within the crystals of 1 and 2. Compound 1 crystallizes as one-dimensional supramolecular chains whereas the crystal packing of 2 consists of a herringbone of sandwiches composed by two inversely related [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] molecules. (c) 2007 Elsevier B.V. All rights reserved.

Determination and statistical treatment of short-circuit currents for faults on the lines of networks of 440 kV CESP system

The distribution of short-circuit current is investigated by means of two methods, one direct and the other analytic; both methods consider uniform probability distribution of line faults. In the direct method, the procedure consists of calculating fault currents at equidistant points along the line, starting from one of the end points and considering the other end open. The magnitude of the current is classified according to Brazilian standards (regulation NBR-7118). The analytic method assumes that the distribution of short-circuit currents through the busbar and the distribution of the line length connected to it are known, as well as the independence of values. The method is designed to determine the probability that fault currents through a line will surpass the pre-established magnitude, thus generating frequency distribution curves of short-circuit currents along the lines.

Investigating effects of neutral wire and grounding in distribution systems with faults

In some applications like fault analysis, fault location, power quality studies, safety analysis, loss analysis, etc., knowing the neutral wire and ground currents and voltages could be of particular interest. In order to investigate effects of neutrals and system grounding on the operation of the distribution feeders with faults, in this research a hybrid short circuit algorithm is generalized. In this novel use of the technique, the neutral wire and assumed ground conductor are explicitly represented. Results obtained from several case studies using IEEE 34-node test network are presented and discussed.