Ultra-trace monitoring of copper in environmental and biological samples by inductively coupled plasma atomic emission spectrometry after separation and preconcentration by using octadecyl silica membrane disks modified by a new schiff's base

Ultra-trace amounts of Cu(II) were separated and preconcentrated by solid phase extraction on octadecyl-bonded silica membrane disks modified with a new Schiff,s base (Bis- (2-Hydroxyacetophenone) -2,2-dimethyl-1,3-propanediimine) (SBTD) followed by elution and inductively coupled plasma atomic emission spectrometric detection. The method was applied as a separation and detection method for copper(II) in environmental and biological samples. Extraction efficiency and the influence of sample matrix, flow rate, pH, and type and minimum amount of stripping acid were investigated. The concentration factor and detection limit of the proposed method are 500 and 12.5 pg mL-1, respectively.

Flow analysis by using solenoid valves for As(III) determination in natural waters by an on-line separation and pre-concentration system coupled to a tungsten coil atomizer

A flow system coupled to a tungsten coil atomizer in an atomic absorption spectrometer (TCA-AAS) was developed for As(III) determination in waters, by extraction with sodium diethyldithiocarbamate (NaDDTC) as complexing agent, and by sorption of the As(III)-DDTC complex in a micro-column filled with 5 mg C18 reversed phase (10 µL dry sorbent), followed by elution with ethanol. A complete pre-concentration/elution cycle took 208 s, with 30 s sample load time (1.7 mL) and 4 s elution time (71 µL). The interface and software for the synchronous control of two peristaltic pumps (RUN/ STOP), an autosampler arm, seven solenoid valves, one injection valve, the electrothermal atomizer and the spectrometer Read function were constructed. The system was characterized and validated by analytical recovery studies performed both in synthetic solutions and in natural waters. Using a 30 s pre-concentration period, the working curve was linear between 0.25 and 6.0 µg L-1 (r = 0.9976), the retention efficiency was 94±1% (6.0 µg L-1), and the pre-concentration coefficient was 28.9. The characteristic mass was 58 pg, the mean repeatability (expressed as the variation coefficient) was 3.4% (n=5), the detection limit was 0.058 µg L-1 (4.1 pg in 71 µL of eluate injected into the coil), and the mean analytical recovery in natural waters was 92.6 ± 9.5 % (n=15). The procedure is simple, economic, less prone to sample loss and contamination and the useful lifetime of the micro-column was between 200-300 pre-concentration cycles.

PARAFAC: uma ferramenta quimiométrica para tratamento de dados multidimensionais. Aplicações na determinação direta de fármacos em plasma humano por espectrofluorimetria

Since the last decade, the combined use of chemometrics and molecular spectroscopic techniques has become a new alternative for direct drug determination, without the need of physical separation. Among the new methodologies developed, the application of PARAFAC in the decomposition of spectrofluorimetric data should be highlighted. The first objective of this article is to describe the theoretical basis of PARAFAC. For this purpose, a discussion about the order of chemometric methods used in multivariate calibration and the development of multi-dimensional methods is presented first. The other objective of this article is to divulge for the Brazilian chemical community the potential of the combination PARAFAC/spectrofluorimetry for the determination of drugs in complex biological matrices. For this purpose, two applications aiming at determining, respectively, doxorrubicine and salicylate in human plasma are presented.

Position sensorless electrically excited synchronous motor drive for industrial use based on direct flux linkage and torque control

Synchronous machines with an AC converter are used mainly in large drives, for example in ship propulsion drives as well as in rolling mill drives in steel industry. These motors are used because of their high efficiency, high overload capacity and good performance in the field weakening area. Present day drives for electrically excited synchronous motors are equipped with position sensors. Most drives for electrically excited synchronous motors will be equipped with position sensors also in future. This kind of drives with good dynamics are mainly used in metal industry. Drives without a position sensor can be used e.g. in ship propulsion and in large pump and blower drives. Nowadays, these drives are equipped with a position sensor, too. The tendency is to avoid a position sensor if possible, since a sensor reduces the reliability of the drive and increases costs (latter is not very significant for large drives). A new control technique for a synchronous motor drive is a combination of the Direct Flux Linkage Control (DFLC) based on a voltage model and a supervising method (e.g. current model). This combination is called Direct Torque Control method (DTC). In the case of the position sensorless drive, the DTC can be implemented by using other supervising methods that keep the stator flux linkage origin centered. In this thesis, a method for the observation of the drift of the real stator flux linkage in the DTC drive is introduced. It is also shown how this method can be used as a supervising method that keeps the stator flux linkage origin centered in the case of the DTC. In the position sensorless case, a synchronous motor can be started up with the DTC control, when a method for the determination of the initial rotor position presented in this thesis is used. The load characteristics of such a drive are not very good at low rotational speeds. Furthermore, continuous operation at a zero speed and at a low rotational speed is not possible, which is partly due to the problems related to the flux linkage estimate. For operation in a low speed area, a stator current control method based on the DFLC modulator (DMCQ is presented. With the DMCC, it is possible to start up and operate a synchronous motor at a zero speed and at low rotational speeds in general. The DMCC is necessary in situations where high torque (e.g. nominal torque) is required at the starting moment, or if the motor runs several seconds at a zero speed or at a low speed range (up to 2 Hz). The behaviour of the described methods is shown with test results. The test results are presented for the direct flux linkage and torque controlled test drive system with a 14.5 kVA, four pole salient pole synchronous motor with a damper winding and electric excitation. The static accuracy of the drive is verified by measuring the torque in a static load operation, and the dynamics of the drive is proven in load transient tests. The performance of the drive concept presented in this work is sufficient e.g. for ship propulsion and for large pump drives. Furthermore, the developed methods are almost independent of the machine parameters.

Salient Pole Synchronous Machine Modelling in an Industrial Direct Torque Controlled Drive Application

Synchronous motors are used mainly in large drives, for example in ship propulsion systems and in steel factories' rolling mills because of their high efficiency, high overload capacity and good performance in the field weakening range. This, however, requires an extremely good torque control system. A fast torque response and a torque accuracy are basic requirements for such a drive. For large power, high dynamic performance drives the commonly known principle of field oriented vector control has been used solely hitherto, but nowadays it is not the only way to implement such a drive. A new control method Direct Torque Control (DTC) has also emerged. The performance of such a high quality torque control as DTC in dynamically demanding industrial applications is mainly based on the accurate estimate of the various flux linkages' space vectors. Nowadays industrial motor control systems are real time applications with restricted calculation capacity. At the same time the control system requires a simple, fast calculable and reasonably accurate motor model. In this work a method to handle these problems in a Direct Torque Controlled (DTC) salient pole synchronous motor drive is proposed. A motor model which combines the induction law based "voltage model" and motor inductance parameters based "current model" is presented. The voltage model operates as a main model and is calculated at a very fast sampling rate (for example 40 kHz). The stator flux linkage calculated via integration from the stator voltages is corrected using the stator flux linkage computed from the current model. The current model acts as a supervisor that prevents only the motor stator flux linkage from drifting erroneous during longer time intervals. At very low speeds the role of the current model is emphasised but, nevertheless, the voltage model always stays the main model. At higher speeds the function of the current model correction is to act as a stabiliser of the control system. The current model contains a set of inductance parameters which must be known. The validation of the current model in steady state is not self evident. It depends on the accuracy of the saturated value of the inductances. Parameter measurement of the motor model where the supply inverter is used as a measurement signal generator is presented. This so called identification run can be performed prior to delivery or during drive commissioning. A derivation method for the inductance models used for the representation of the saturation effects is proposed. The performance of the electrically excited synchronous motor supplied with the DTC inverter is proven with experimental results. It is shown that it is possible to obtain a good static accuracy of the DTC's torque controller for an electrically excited synchronous motor. The dynamic response is fast and a new operation point is achieved without oscillation. The operation is stable throughout the speed range. The modelling of the magnetising inductance saturation is essential and cross saturation has to be considered as well. The effect of cross saturation is very significant. A DTC inverter can be used as a measuring equipment and the parameters needed for the motor model can be defined by the inverter itself. The main advantage is that the parameters defined are measured in similar magnetic operation conditions and no disagreement between the parameters will exist. The inductance models generated are adequate to meet the requirements of dynamically demanding drives.

Preparative separation of flavonoids from the medicinal plant Davilla elliptica St. Hill. by high-speed counter-current chromatography

High-speed counter-current chromatography (HSCCC) is a major tool for the fast separation of natural products from plants. It was used for the preparative isolation of the flavonoid monoglucosides present in the aerial parts of the Davilla elliptica St. Hill. (Dilleniaceae). This species is used in Brazilian folk medicine for the treatment of gastric disorders. The optimum solvent system used was composed of a mixture of ethyl acetate-n-propanol-water (140:8:80, v/v/v) and led to a successful separation of quercetin-3-O-alpha-L-rhamnopyranoside and myricetin-3-O-alpha-L-rhamnopyranoside in approximately 3.0 hours with purity higher than 95%. Identification was performed by ¹H NMR, 13C NMR and HPLC-UV-DAD analyses.

Intracellular membrane trafficking in Osteoclasts The role of direct Rab protein – Rac 1 interactions in the targeting of intracellular vesicles

Osteoclasts are cells responsible for bone resorption. These cells undergo extensive membrane re-organization during their polarization for bone resorption and form four distinct membrane domains, namely the ruffled border, the basolateral membrane, the sealing zone and the functional secretory domain. The endocytic/biosynthetic pathway and transcytotic route(s) are important for the resorption process, since the endocytic/biosynthetic pathway brings the specific vesicles to the ruffled border whereas the transcytotic flow is believed to transport the degraded bone matrix away from the resorption lacuna to the functional secretory domain. In the present study, we found a new transcytotic route from the functional secretory domain to the ruffled border, which may compensate membrane loss from the ruffled border during the resorption process. We also found that lipid rafts are essential for the ruffled border-targeted late endosomal pathways. A small GTP-binding protein, Rab7, has earlier been shown to regulate the late steps of the endocytic pathway. In bone-resorbing osteoclasts it is involved in the formation of the ruffled border, which displays several features of late endosomal membranes. Here we discovered a new Rab7-interacting protein, Rac1, which is another small GTP-binding protein and binds to the GTP-form of Rab7 in vitro. We demonstrated further that Rab7 colocalizes with Rac1 at the fusion zone of the ruffled border in bone-resorbing osteoclasts. In other cell types, such as fibroblast-like cells, this colocalization is mainly perinuclear. Because Rac1 is known to control the actin cytoskeleton through its effectors, we suggest that the Rab7-Rac1 interaction may mediate late endosomal transport between microtubules and microfilaments, thus enabling endosomal vesicles to switch tracks from microtubules to microfilaments before their fusion to the ruffled border. We then studied the role of Rab-Rac1 interaction in the slow recycling pathway. We revealed that Rac1 also binds directly to Rab11 and to some other but not all Rab-proteins, suggesting that Rab-Rac1 interaction could be a general regulatory mechanism to direct the intracellular vesicles from microtubule mediated transport to actin filament mediated transport and vice versa. On the basis of our results we thus propose a new hypothesis for these GTPases in the regulation of intracellular membrane flow.

Cyclin-dependent kinases 4 and 6 control tumor progression and direct glucose oxidation in the pentose cycle

Cyclin-dependent kinases CDK4 and CDK6 are essential for the control of the cell cycle through the G1 phase. Aberrant expression of CDK4 and CDK6 is a hall- mark of cancer, which would suggest that CDK4 and CDK6 are attractive targets for cancer therapy. Herein, we report that calcein AM is a potent specific inhibitor of CDK4 and CDK6 in HCT116 human colon adenocarcinoma cells, inhibiting retinoblastoma protein (pRb) phosphorylation and inducing cell cycle arrest in the G1 phase. The metabolic effects of calcein AM (the calcein acetoxymethyl-ester) on HCT116 cells were also evaluated and the flux between the oxidative and non-oxidative branches of the pentose phos-phate pathway was significantly altered. To elucidate whe-ther these metabolic changes were due to the inhibition of CDK4 and CDK6, we also characterized the metabolic profile of a CDK4, CDK6 and CDK2 triple knockout of mouse embryonic fibroblasts. The results show that the metabolic profile associated with the depletion of CDK4, CDK6 and CDK2 coincides with the metabolic changes induced by calcein AM on HCT116 cells, thus confirming that the inhibition of CDK4 and CDK6 disrupts the balance between the oxidative and non-oxidative branches of the pentose phosphate pathway. Taken together, these results indicate that low doses of calcein can halt cell division and kill tumor cells. Thus, selective inhibition of CDK4 and CDK6 may be of greater pharmacological interest, since inhibitors of these kinases affect both cell cycle progression and the robust metabolic profile of tumors.

Efeitos dos parâmetros operacionais na fotodegradação do azo corante direct red 23 na interface dióxido de titânio/água

The decolorization and degradation of direct red 23 azo dye have been investigated in aqueous suspension of titanium dioxide under artificial irradiation. The effects of some operational parameters such as azo dye concentration, catalyst loading, and solution pH were investigated at 30.0 ºC and optimized values were obtained. The first-order kinetic model was used to discuss the results. The UV-Vis spectra changes showed that the azo dye sample, collected after 6 h irradiation, was 98% decolorized while the residual total carbon was 97.9% degraded, indicating simultaneous photodecolorization and degradation.

An easy and direct method for the synthesis of 1,2,4-triazole derivatives through carboxylic acids and hydrazinophthalazine

We have developed an easy method for the synthesis of thirteen compounds derived from 1,2,4-triazoles through a carboxylic acid and hydrazinophthalazine reaction, with a 75-85% yield mediated by the use of agents such as 1-ethyl-3-(3'-dimethylaminopropyl)-carbodiimide hydrochloride and 1-hydroxybenzotriazole. The operational simplicity of this method and the good yield of products make it valuable for the synthesis of new compounds with pharmacological activity.

Effects of Surface Properties and Wood Modification into Direct Printing on Wood

Building industry is a high volume branch which could provide prominent markets for wood based interior decoration solutions. Competition in interior decoration markets requires versatility in appearance. Versatility in wood appearance and added value could be achieved by printing grain patterns of different species or images directly onto wood. The problem when planning wood printing’s implementing into durable applications is basically how to transfer a high quality image or print sustainably onto wood, which is porous, heterogeneous, dimensionally unstable, non-white and rough. Wood preservation or treating, and modification can provide durability against degradation but also effect to the surface properties of wood which will effect on printability. Optimal adhesion is essential into print quality, as too high ink absorbance can cause spreading and too low ink absorbance cause pale prints. Different printing techniques have different requirements on materials and production. The direct printing on wood means, that intermedias are not used. Printing techniques with flexible printing plates or in fact non-impact techniques provide the best basis for wood printing. Inkjet printing of wood with different mechanical or chemical surface treatments, and wood plastic composite material gave good results that encourage further studies of the subject. Sanding the wood surface anti-parallel to the grain gave the best overall printing quality. Spreading parallel to the grain could not be avoided totally, except in cases where wood was treated hydrophobic so adhesion of the ink was not sufficient. Grain pattern of the underlying wood stays clearly visible in the printed images. Further studies should be made to fine tune the methods that already gave good results. Also effects of moisture content of wood, different inks, and long-term exposure to UV-radiation should be tested.

The influence of crystallization conditions on the filtration characteristics of sulphathiazole suspensions

Cooling crystallization is one of the most important purification and separation techniques in the chemical and pharmaceutical industry. The product of the cooling crystallization process is always a suspension that contains both the mother liquor and the product crystals, and therefore the first process step following crystallization is usually solid-liquid separation. The properties of the produced crystals, such as their size and shape, can be affected by modifying the conditions during the crystallization process. The filtration characteristics of solid/liquid suspensions, on the other hand, are strongly influenced by the particle properties, as well as the properties of the liquid phase. It is thus obvious that the effect of the changes made to the crystallization parameters can also be seen in the course of the filtration process. Although the relationship between crystallization and filtration is widely recognized, the number of publications where these unit operations have been considered in the same context seems to be surprisingly small. This thesis explores the influence of different crystallization parameters in an unseeded batch cooling crystallization process on the external appearance of the product crystals and on the pressure filtration characteristics of the obtained product suspensions. Crystallization experiments are performed by crystallizing sulphathiazole (C9H9N3O2S2), which is a wellknown antibiotic agent, from different mixtures of water and n-propanol in an unseeded batch crystallizer. The different crystallization parameters that are studied are the composition of the solvent, the cooling rate during the crystallization experiments carried out by using a constant cooling rate throughout the whole batch, the cooling profile, as well as the mixing intensity during the batch. The obtained crystals are characterized by using an automated image analyzer and the crystals are separated from the solvent through constant pressure batch filtration experiments. Separation characteristics of the suspensions are described by means of average specific cake resistance and average filter cake porosity, and the compressibilities of the cakes are also determined. The results show that fairly large differences can be observed between the size and shape of the crystals, and it is also shown experimentally that the changes in the crystal size and shape have a direct impact on the pressure filtration characteristics of the crystal suspensions. The experimental results are utilized to create a procedure that can be used for estimating the filtration characteristics of solid-liquid suspensions according to the particle size and shape data obtained by image analysis. Multilinear partial least squares regression (N-PLS) models are created between the filtration parameters and the particle size and shape data, and the results presented in this thesis show that relatively obvious correlations can be detected with the obtained models.

Development of a flotation method for preconcentration-separation of trace amounts of some metal ions in plant tissues prior to their FAAS determinations

An efficient flotation method based on the combination of flame atomic absorption spectrometry (FAAS) and separation and preconcentration step for determination of Cr3+, Cu 2+, Co2+, Ni2+, Zn2+, Cd 2+, Fe3+ and Pb2+ ions in various real samples by the possibility of applying bis(2-hydroxyacetophenone)-1,4-butanediimine (BHABDI) as a new collector was studied. The influence of pH, amount of BHABDI as collector, sample matrix, type and amount of eluting agent, type and amount of surfactant as floating agent, ionic strength and air flow rates i.e. variables affecting the efficiency of the extraction system was evaluated. It is ascertained that metal ions such as iron can be separated simultaneously from matrix in the presence of 0.012 mM ligand, 0.025% (w/v) of CTAB to a test sample of 750 mL at pH 6.5. These ions can be eluted quantitatively with 6 mL of 1.0 mol L-1 HNO3 in methanol which lead to the enrichment factor of 125. The detection limits for analyte ions were in the range of 1.3-2.4 ng mL-1. The method has been successfully applied for determination of trace amounts of ions in various real samples.

Separation and preconcentration trace amounts of gold by using modified organo nanoclay closite 15A

The application of organo nanoclay 5-(4-dimethylamino-benzylidene) rhodanine-immobilized as a new, easily prepared, and stable solid sorbent for preconcentration trace amounts of Au(III) ions in aqueous solution is presented. The sorption of Au(III) ions was quantitative in the pH range of 2-4, and quantitative desorption occurred instantaneously with 10.0 mL of a mixture containing 0.5 mol L-1 Na2S2O3 and KSCN. Various parameters, such as the effect of pH, breakthrough volume, extraction time, and interference of a large number of anions and cations have been studied. The proposed method has been applied for determination of trace amount of gold in water samples.

A comparison of electrodeposited Ti/β-PbO2 and Ti-Pt/β-PbO2 anodes in the electrochemical degradation of the direct yellow 86 dye

The electrochemical performance of electrodeposited Ti/β-PbO2 and Ti-Pt/β-PbO2 anodes was galvanostatically evaluated (batch mode, 50 mA cm-2) to degrade the Direct Yellow 86 dye (100 or 200 mg L-1 in 0.1 mol L-1 Na2SO4 + 1.5 g L-1 NaCl), investigating the effect of pH and temperature. Similar results were obtained for both electrodes and the best conditions for removal of color and chemical oxygen demand are pH 7 and 40 °C, when 90% decolorization is attained by passing a charge of only ~0.13 A h L-1 and total mineralization is achieved with expenditure of ~5 kW h m-3.