(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.

Complete assignment of (1)H and (13)C NMR spectra of alpha-phenylsulfinyl-N-methoxy-N-methylpropionamide and some p-substituted derivatives

The complete assignment of the (1)H and (13)C NMR spectra of the diastereomeric pairs of some alpha-arylsulfinyl-substituted N-methoxy-N-methylpropionamides with the substituents methoxy, methyl, chloro, nitro is reported. Copyright (C) 2008 John Wiley & Sons, Ltd.

Catalytic ethanolysis of soybean oil with immobilized lipase from Candida antarctica and (1)H NMR and GC quantification of the ethyl esters (biodiesel) produced

The catalytic ethanolysis of soybean oil with commercial immobilized lipase type B from Candida antarctica to yield ethyl esters (biodiesel) has been investigated. Transesterification was monitored with respect to the following parameters: quantity of biocatalyst, reaction time, amount of water added and turnover of lipase. The highest yields of biodiesel (87% by (1)H NMR; 82.9% by GC) were obtained after a reaction time of 24 h at 32 degrees C in the presence of lipase equivalent to 5.0% (w/w) of the amount of soybean oil present. The production of ethyl esters by enzymatic ethanolysis was not influenced by the addition of water up to 4.0% (v/v) of the alcohol indicating that it is possible to use hydrated ethanol in the production of biodiesel catalyzed by lipase. The immobilized enzyme showed high stability under moderate reaction conditions and retained its activity after five production cycles. The (1)H NMR methodology elaborated for the quantification of biodiesel in unpurified reaction mixtures showed good correlations between the signal areas of peaks associated with the alpha-methylene groups of the ethyl esters and those of the triacyl-glycerides in residual soybean oil. Monoacylglycerides, diacylglycerides and triglycerides could also be detected and quantified in the crude biodiesel using (1)H NMR spectroscopic and GC-FID chromatographic methods. The biodiesel production by enzymatic catalysis was promising. In this case, was produced a low concentration of glycerol (0.74%) and easily removed by water extraction. (C) 2010 Elsevier B.V. All rights reserved.

Fast Acquisition of (13)C NMR Spectra using the Steady-state Free Precession Sequence

In this paper, we show that the steady-state free precession sequence can be used to acquire (13)C high-resolution nuclear magnetic resonance spectra and applied to qualitative analysis. The analysis of brucine sample using this sequence with 60 degrees flip angle and time interval between pulses equal to 300 ms (acquisition time, 299.7 ms; recycle delay, 300 ms) resulted in spectrum with twofold enhancement in signal-to-noise ratio, when compared to standard (13)C sequence. This gain was better when a much shorter time interval between pulses (100 ms) was applied. The result obtained was more than fivefold enhancement in signal-to-noise ratio, equivalent to more than 20-fold reduction in total data recording time. However, this short time interval between pulses produces a spectrum with severe phase and truncation anomalies. We demonstrated that these anomalies can be minimized by applying an appropriate apodization function and plotting the spectrum in the magnitude mode.

Performance Evaluation of Different PV-Array Configurations under Weak Light Conditions and Partial Shadings

The paper analyses empirical performance data of five commercial PV-plants in Germany. The purpose was on one side to investigate the weak light performance of the different PV-modules used. On the other hand it was to quantify and compare the shading losses of different PV-array configurations. The importance of this study relies on the fact that even if the behavior under weak light conditions or the shading losses might seem to be a relatively small percentage of the total yearly output; in projects where a performance guarantee is given, these variation can make the difference between meeting or not the conditions.When analyzing the data, a high dispersion was found. To reduce the optical losses and spectral effects, a series of data filters were applied based on the angle of incidence and absolute Air Mass. To compensate for the temperature effects and translate the values to STC (25°C), five different methods were assessed. At the end, the Procedure 2 of IEC 60891 was selected due to its relative simplicity, usage of mostly standard parameters found in datasheets, good accuracy even with missing values, and its potential to improve the results when the complete set of inputs is available.After analyzing the data, the weak light performance of the modules did not show a clear superiority of a certain technology or technology group over the others. Moreover, the uncertainties in the measurements restrictive the conclusiveness of the results.In the partial shading analysis, the landscape mounting of mc-Si PV-modules in free-field showed a significantly better performance than the portrait one. The cross-table string using CIGS modules did not proved the benefits expected and performed actually poorer than a regular one-string-per-table layout. Parallel substrings with CdTe showed a proper functioning and relatively low losses. Among the two product generations of CdTe analyzed, none showed a significantly better performance under partial shadings.

COMPARISON OF PARTIAL SHADING LOSSES IN FREE FIELD PV-PLANTS WITH DIFFERENT ARRAY CONFIGURATIONS

A common problem when planning large free field PV-plants is optimizing the ground occupation ratio while maintaining low shading losses. Due to the complexity of this task, several PV-plants have been built using various configurations. In order to compare the shading losses of different PV technologies and array designs, empirical performance data of five free field PV-plants operating in Germany was analyzed. The data collected comprised 140 winter days from October 2011 until March 2012. The relative shading losses were estimated by comparing the energy output of selected arrays in the front rows (shading-free) against that of shaded arrays in the back rows of the same plant. The results showed that landscape mounting with mc-Si PV-modules yielded significantly better results than portrait one. With CIGS modules, making cross-table strings using the lower modules was not beneficial as expected and had more losses than a one-string-per-table layout. Parallel substrings with CdTe showed relatively low losses. Among the two CdTe products analyzed, none showed a significantly better performance.

Mixed-signal analog-digital circuits design on the pre-diffused digital array using trapezoidal association of transistors

The mixed-signal and analog design on a pre-diffused array is a challenging task, given that the digital array is a linear matrix arrangement of minimum-length transistors. To surmount this drawback a specific discipline for designing analog circuits over such array is required. An important novel technique proposed is the use of TAT (Trapezoidal Associations of Transistors) composite transistors on the semi-custom Sea-Of-Transistors (SOT) array. The analysis and advantages of TAT arrangement are extensively analyzed and demonstrated, with simulation and measurement comparisons to equivalent single transistors. Basic analog cells were also designed as well in full-custom and TAT versions in 1.0mm and 0.5mm digital CMOS technologies. Most of the circuits were prototyped in full-custom and TAT-based on pre-diffused SOT arrays. An innovative demonstration of the TAT technique is shown with the design and implementation of a mixed-signal analog system, i. e., a fully differential 2nd order Sigma-Delta Analog-to-Digital (A/D) modulator, fabricated in both full-custom and SOT array methodologies in 0.5mm CMOS technology from MOSIS foundry. Three test-chips were designed and fabricated in 0.5mm. Two of them are IC chips containing the full-custom and SOT array versions of a 2nd-Order Sigma-Delta A/D modulator. The third IC contains a transistors-structure (TAT and single) and analog cells placed side-by-side, block components (Comparator and Folded-cascode OTA) of the Sigma-Delta modulator.

Use of novel biomarkers (Homocysteine, vitamin B6, B9 and B12) on the assessing the progression of cardiovascular disease

A large number of evidences correlate elevated levels of homocysteine (Hcys) with a higher cardiovascular diseases (CVDs) risk, especially, atherosclerosis. Similarly, abnormal low levels of the vitamins B6, B9 and B12 are associated to an instability in the methionine cycle with an over production of Hcys. Thus, biomedical sciences are looking forward for a cheaper, faster, precise and accurate analytical methodology to quantify these compounds in a suitable format for the clinical environment. Therefore the objective of this study was the development of a simple, inexpensive and appropriate methodology to use at the clinical level. To achieve this goal, a procedure integrating a digitally controlled (eVol®) microextraction by packed sorbent (MEPS) and an ultra performance liquid chromatography (UPLC) coupled to a photodiode array detector (PDA) was developed to identify and quantify Hcys vitamins B6, B9 and B12. Although different conditions were assayed, we were not able to combine Hcys with the vitamins in the same analytical procedure, and so we proceeded to the optimization of two methods differing only in the composition of the gradient of the mobile phase and the injected volume. It was found that MEPS did not bring any benefit to the quantification of the Hcys in the plasma. Therefore, we developed and validate an alternative method that uses the direct injection of treated plasma (reduced and precipitated). This same method was evaluated in terms of selectivity, linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect and precision (intra-and inter-day) and applied to the determination of Hcys in a group composed by patients presenting augmented CVD risk. Good results in terms of selectivity and linearity (R2> 0.9968) were obtained, being the values of LOD and LOQ 0.007 and 0.21 mol / L, respectively. The intra-day precision (1.23-3.32%), inter-day precision (5.43-6.99%) and the recovery rate (82.5 to 93.1%) of this method were satisfactory. The matrix effect (>120%) was, however, higher than we were waiting for. Using this methodology it was possible to determine the amount of Hcys in real plasma samples from individuals presenting augmented CVD risk. Regarding the methodology developed for vitamins, despite the optimization of the extraction technique and the chromatographic conditions, it was found that the levels usually present in plasma are far below the sensitivity we obtained. Therefore, further optimizations of the methodology developed are needed. As conclusion, part of the objectives of this study was achieved with the development of a quick, simple and cheaper method for the quantification of Hcys.

Preferential location of lidocaine and etidocaine in lecithin bilayers as determined by EPR, fluorescence and H-2 NMR

We have examined the effect of the uncharged species of lidocaine (LDC) and etidocaine (EDC) on the acyl chain moiety of egg phosphatidylcholine liposomes. Changes in membrane organization caused by both anesthetics were detected through the use of EPR spin labels (5, 7 and 12 doxyl stearic acid methyl ester) or fluorescence probes (4, 6, 10, 16 pyrene-fatty acids). The disturbance caused by the LA was greater when the probes were inserted in more external positions of the acyl chain and decreased towards the hydrophobic core of the membrane. The results indicate a preferential insertion of LDC at the polar interface of the bilayer and in the first half of the acyl chain, for EDC. Additionally, 2 H NMR spectra of multilamellar liposomes composed by acyl chain-perdeutero DMPC and EPC (1:4 mol%) allowed the determination of the segmental order (S-mol) and dynamics (T-1) of the acyl chain region. In accordance to the fluorescence and EPR results, changes in molecular orientation and dynamics are more prominent if the LA preferential location is more superficial, as for LDC while EDC seems to organize the acyl chain region between carbons 2-8, which is indicative of its positioning. We propose that the preferential location of LDC and EDC inside the bilayers creates a "transient site", which is related to the anesthetic potency since it could modulate the access of these molecules to their binding site(s) in the voltage-gated sodium channel. (C) 2007 Elsevier B.V. All rights reserved.

A novel system for large-scale gene expression analysis: bacterial colonies array

In the present work, we report the use of bacterial colonies to optimize macroarray technique. The devised system is significantly cheaper than other methods available to detect large-scale differential gene expression. Recombinant Escherichia coli clones containing plasmid-encoded copies of 4,608 individual expressed sequence tag (ESTs) were robotically spotted onto nylon membranes that were incubated for 6 and 12 h to allow the bacteria to grow and, consequently, amplify the cloned ESTs. The membranes were then hybridized with a beta-lactamase gene specific probe from the recombinant plasmid and, subsequently, phosphorimaged to quantify the microbial cells. Variance analysis demonstrated that the spot hybridization signal intensity was similar for 3,954 ESTs (85.8%) after 6 h of bacterial growth. Membranes spotted with bacteria colonies grown for 12 h had 4,017 ESTs (87.2%) with comparable signal intensity but the signal to noise ratio was fivefold higher. Taken together, the results of this study indicate that it is possible to investigate large-scale gene expression using macroarrays based on bacterial colonies grown for 6 h onto membranes.

Aplicações de arranjos de antenas de microfita com patch supercondutor

This work has as main objective the study of arrays of microstrip antennas with superconductor rectangular patch. The phases and the radiation patterns are analyzed. A study of the main theories is presented that explain the microscopic and macroscopic phenomena of superconductivity. The BCS, London equations and the Two Fluid Model, are theories used in the applications of superconductors, at the microstrip antennas and antennas arrays. Phase Arrangements will be analyzed in linear and planar configurations. The arrangement factors of these configurations are obtained, and the phase criteria and the spacing between the elements, are examined in order to minimize losses in the superconductor, compared with normal conductors. The new rectangular patch antenna, consist of a superconducting material, with the critical temperature of 233 K, whose formula is Tl5Ba4Ca2Cu9Oy, is analyzed by the method of the Transverse nTransmission Line (TTL), developed by H. C. C. Fernandes, applied in the Fourier Transform Domain (FTD). The TTL is a full-wave method, which has committed to obtaining the electromagnetic fields in terms of the transverse components of the structure. The inclusion of superconducting patch is made using the complex resistive boundary condition, using the impedance of the superconductor in the Dyadic Green function, in the structure. Results are obtained from the resonance frequency depending on the parameters of the antenna using superconducting material, radiation patterns in E-Plane and H -Plane, the phased antennas array in linear and planar configurations, for different values of phase angles and different spacing between the elements

Contribuição para o estudo do embarque de uma rede neural artificial em field programmable gate array (FPGA)

This study shows the implementation and the embedding of an Artificial Neural Network (ANN) in hardware, or in a programmable device, as a field programmable gate array (FPGA). This work allowed the exploration of different implementations, described in VHDL, of multilayer perceptrons ANN. Due to the parallelism inherent to ANNs, there are disadvantages in software implementations due to the sequential nature of the Von Neumann architectures. As an alternative to this problem, there is a hardware implementation that allows to exploit all the parallelism implicit in this model. Currently, there is an increase in use of FPGAs as a platform to implement neural networks in hardware, exploiting the high processing power, low cost, ease of programming and ability to reconfigure the circuit, allowing the network to adapt to different applications. Given this context, the aim is to develop arrays of neural networks in hardware, a flexible architecture, in which it is possible to add or remove neurons, and mainly, modify the network topology, in order to enable a modular network of fixed-point arithmetic in a FPGA. Five synthesis of VHDL descriptions were produced: two for the neuron with one or two entrances, and three different architectures of ANN. The descriptions of the used architectures became very modular, easily allowing the increase or decrease of the number of neurons. As a result, some complete neural networks were implemented in FPGA, in fixed-point arithmetic, with a high-capacity parallel processing

A comparative solid state C-13 NMR and thermal study of CO2 capture by amidines PMDBD and DBN

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

Sensor array made with nanostructured films to detect a phenothiazine compound

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

Ab initio study and NMR analysis of the complexion of citric acid with ion lithium

Quantum mechanics calculations at the ab initio HF/3-21G* level were carried out with Nuclear Magnetic Resonance (NMR) measurements to characterize citric acid and lithium interactions. The results indicate the formation of a tridentate organometallic compound with one lithium and one citric acid molecule and a tridentate and bidentate compound of two lithium atoms and one citric acid molecule. The results are in agreement with the experimental and theoretical data. (C) 1999 Elsevier B.V. B.V. All rights reserved.