Capillary siphons and their application in the fuel delivery system of direct methanol fuel cells

The objective of the work is to develop a fuel delivery system for potable direct methanol fuel cell. Currently, one of the most fundamental limitations of direct methanol fuel cells is that the fuel supplied to the anode of the DMFC must be a very dilute aqueous methanol solution (usually 0.5∼1.5 M). If a DMFC is filled with a dilute aqueous methanol solution, the fuel cell operation time per refuel would be very short, which would considerably diminish the advantage of a DMFC over a conventional battery. To overcome this difficulty, a complex fuel delivery system based on the modern micro system technology was proposed by the author. The proposed fuel delivery system would include micro-pumps, a methanol sensor, and a control unit. The fuel delivery system adds considerable costs to the fuel cell system and consume considerable amount of electricity from the fuel cell, which in turn significantly reduces the net power output of the fuel cell. As a result, the DMFC would have tremendous difficulty to compete with the conventional battery technology in terms of costs and power output. ^ This work presents a novel passive fuel delivery system for direct methanol fuel cells. In this particular system, a methanol fuel and an aqueous methanol solution are stored separately in two containers and a wick is disposed between the two containers in a siphon fashion, with the container of the aqueous methanol solution communicating with the anode of the DMFC. Methanol is siphoned from the methanol container to the aqueous solution container in-situ when the methanol in the aqueous methanol solution is consumed during the operation of the fuel cell. Through a proper selection of the wick and the containers, the methanol concentration near the anode of the DMFC could be maintained within a preferable range. ^

Synthesis and characterization of photochromic indolyl substituted fulgides and fulgimides

The fulgide and fulgimide family constitutes an important class of organic photochromic compounds. The ability of fulgides and fulgimides to interconvert between two key forms by irradiation of different wavelength of light has made them promising material in optical memory devices, optical switches and sensors, and specialty dyes and inks. Thermal stability and hydrolytic stability of fulgides and fulgimides are essential for their practical applications. A deuterated trifluoromethyl indolylfulgide was synthesized based on the synthetic pathway of the proteo trifluoromethyl indolylfulgide using commercially available deuterated starting materials. Deuteration of the isopropylidene group improved the thermal stability of the indolylfulgide by a factor of 7. ^ Fulgimides are the most important fulgide derivatives. Fulgimides improve the hydrolytic stability of fulgides by replacing the succinic anhydride ring with a succinimide ring. A novel trifluoromethyl N-ethoxycarbonylmethyl indolylfulgimide was synthesized from trifluoromethyl indolylfulgide. The trifluoromethyl indolylfulgide was synthesized on a large scale in five steps with an overall yield of 18%. The indolylfulgide was then converted to indolylfulgimide by aminolysis follow by dehydration. The N-ethoxycarbonylmethyl indolylfulgimide showed enhanced hydrolytic stability and photochemical stability in 70/30 ethanol/water. ^ Three novel aqueous soluble fulgimides, trifluoromethyl carboxylic acid indolylfulgimide, dicarboxylic acid indolylfulgimide, and H-carboxylic acid indolylfulgimide, were synthesized. In sodium phosphate buffer (pH 7.4) at 37 ºC, an unusual hydrolysis of the trifluoromethyl group of the closed form of the carboxylic acid indolylfulgimide resulted in the dicarboxylic acid indolylfulgimide which has an additional carboxylic acid group. The closed form of dicarboxylic acid indolylfulgimide was further decarboxylated to generate H-carboxylic acid indolylfulgimide which was not photochromic. The trifluoromethyl dicarboxylic acid indolylfulgimide is the most robust fulgimide yet reported in aqueous solution. ^ A novel aqueous soluble methyl carboxylic acid indolylfulgimide was synthesized from methyl indolylfulgide. The methyl indolylfulgide was synthesized in five steps with an overall yield of 21%. The methyl carboxylic acid indolylfulgimide was synthesized by aminolysis follow by dehydration. The methyl carboxylic acid indolylfulgimide is expected to have improved thermal and photochemical stability in aqueous solutions relative to the trifluoromethyl analog.^

Development of a surface-enhanced raman spectroscopy method for the detection of benzodiazepines in urine

Benzodiazepines are among the most prescribed compounds for anti-anxiety and are present in many toxicological screens. These drugs are also prominent in the commission of drug facilitated sexual assaults due their effects on the central nervous system. Due to their potency, a low dose of these compounds is often administered to victims; therefore, the target detection limit for these compounds in biological samples is 10 ng/mL. Currently these compounds are predominantly analyzed using immunoassay techniques; however more specific screening methods are needed. ^ The goal of this dissertation was to develop a rapid, specific screening technique for benzodiazepines in urine samples utilizing surface-enhanced Raman spectroscopy (SERS), which has previously been shown be capable of to detect trace quantities of pharmaceutical compounds in aqueous solutions. Surface enhanced Raman spectroscopy has the advantage of overcoming the low sensitivity and fluorescence effects seen with conventional Raman spectroscopy. The spectra are obtained by applying an analyte onto a SERS-active metal substrate such as colloidal metal particles. SERS signals can be further increased with the addition of aggregate solutions. These agents cause the nanoparticles to amass and form hot-spots which increase the signal intensity. ^ In this work, the colloidal particles are spherical gold nanoparticles in aqueous solution with an average size of approximately 30 nm. The optimum aggregating agent for the detection of benzodiazepines was determined to be 16.7 mM MgCl2, providing the highest signal intensities at the lowest drug concentrations with limits of detection between 0.5 and 127 ng/mL. A supported liquid extraction technique was utilized as a rapid clean extraction for benzodiazepines from urine at a pH of 5.0, allowing for clean extraction with limits of detection between 6 and 640 ng/mL. It was shown that at this pH other drugs that are prevalent in urine samples can be removed providing the selective detection of the benzodiazepine of interest. ^ This technique has been shown to provide rapid (less than twenty minutes), sensitive, and specific detection of benzodiazepines at low concentrations in urine. It provides the forensic community with a sensitive and specific screening technique for the detection of benzodiazepines in drug facilitated assault cases.^

Obtenção de organovermiculitas utilizando tensoativos e microemulsões e suas aplicações na separação de isômeros do Xileno

Surfactants are versatile organic compounds that have, in a single molecule, double chemical affinity. The surfactant molecule is composed by a hy drophobic tail group, a hydrocarbon chain (linear, branched, or mixed), and by a hydrophilic head group, which contains polar groups that makes it able to be applied in the organophilization process of natural clays. Microemulsions are microheterogeneous b lends composed by: a surfactant, an oily phase (non - polar solvent), an aqueous phase, and, sometimes, a co - surfactant (short - chain alcohol). They are systems with thermodynamic stability, transparent, and have high solubility power. Vermiculite is a clay m ineral with an expandable crystalline structure that has high cation exchange capacity. In this work vermiculite was used to obtain organoclays. The ionic surfactants dodecyl ammonium chlori de (DDAC) and cetyltrimethylammonium bromide (C 16 TAB) were used in the organophilization process. They were used as surfactant aqueous solutions and, for DDAC, as a microemulsion system. The organoclays were used to promote the separation of binary mixtures of xylene isomers (ortho - and meta - xylene). Dif ferent analytical techniques were used to characterize microemulsion systems and also the nanoclays. It was produced a water - rich microemulsion system with 0.92 nm droplet average diameter. The vermiculite used in this work has a cationic exchange capacity of 172 meq/100g and magnesium as main cation (24.25%). The basal spacing of natural vermiculite and organo - vermiculites were obtained by X - ray Diffraction technique. The basal spacing was 1.48nm for natural vermiculite, 4.01nm for CTAB - vermiculite (CTAB 4 ) , and 3.03nm for DDAC - vermiculite (DDAC M1A), that proves the intercalation process. Separation tests were carried out in glass columns using three binary mixtures of xylene (ortho - xylene and meta - xylene). The results showed that the organovermiculite pre sented an enhanced chemical affinity by the mixture of hydrocarbons, when compared with the natural vermiculite, and also its preference by ortho - xylene. A factorial experimental design 2 2 with triplicate at the central point was used to optimize the xylen e separation process. The experimental design revealed that the initial concentration of isomers in the mixture and the mass of organovermiculite were the significant factors for an improved separation of isomers. In the experiments carried out using a bin ary mixture of ortho - xylene and meta - xylene (2:1), after its percolating through the organovermiculite bed (DDAC M1), it was observed the preference of the organoclay by the ortho - xylene isomer, which was retained in greater quantity than the meta - xylene o ne. At the end of the treatment, it was obtained a final concentration in meta - xylene of 47.52%.

Fluidos de perfuração aquosos: a contribuição da goma xantana e carboximetilcelulose no controle de filtrado

This study aimed mainly to evaluate the influence of xanthan gum (XG) and carboxymethylcellulose (CMC) in the filtration process of water-based drilling fluids, considering the conformational changes suffered by the polyelectrolyte with the addition of sodium chloride (NaCl) in different concentrations (0.17, 0.34 and 0.51 mol.L-1). It was also evaluated the behavior of the fluid by the addition of calcium carbonate (CaCO3) in pure water and in brine. Seeking a better understanding of the interaction between the polymers used and CaCO3, polymer adsorption analyzes were performed using a depletion method, which yielded a higher percentage of adsorption of Xanthan Gum in this material (29%), which can justify the formation of a thin and waterproof filter cake for drilling fluids containing this polymer. However, the best values of apparent viscosity (20 and 24 mPa.s) and volume of filtrate (8.0 and 8.1 mL) were obtained for the systems consisting of xanthan gum, CMC and CaCO3, in NaCl aqueous solutions concentrations of 0.34 and 0.51 mol.L-1, respectively. The values can be related to the presence of CMC that increases the apparent viscosity and reduces the volume of filtrate. In addition, the CaCO3 added acts as a bridging agent, promoting the formation of a less permeable filter cake

Efeito da força iônica nas propriedades de fluidos de perfuração aquosos à base de polímeros carboxilados e sulfatados

In the well drilling operations problems caused by contamination of the drilling fluid are common. The dissolution of ions from the geological formations affects the rheological and filtration properties of the fluids. These ions shield the charges of ionic polymers, leading to its precipitation. In this work was performed a detailed study on the stability of the properties of aqueous solutions and aqueous drilling fluids in the presence of sulphated and carboxylated polymers, using carboxymethylcellulose and kappa-carrageenan as polymer compounds carboxylated and sulfated model, respectively. The effects of ionic strength of the aqueous medium containing Na+, Mg2+ and Ca2+ on rheological properties of the polymer and drilling fluids solutions were evaluated by varying the concentration of salts, pH and temperature. It was observed that the fluids with κ-carrageenan suffered less influence against the contamination by the ions at pH 9 to 10, even at higher concentrations, but higher influence on pH> 11. The fluids containing carboxymethylcellulose were more sensitive to contamination, with rapid reduction in viscosity and significant increase of the filtrate volume, while the fluid based polymer sulfated kappa-carrageenan showed evidence of interaction with cations and preserve the rheological properties and improved stability the volume of filtrate.

Efeito da força iônica nas propriedades de fluidos de perfuração aquosos à base de polímeros carboxilados e sulfatados

In the well drilling operations problems caused by contamination of the drilling fluid are common. The dissolution of ions from the geological formations affects the rheological and filtration properties of the fluids. These ions shield the charges of ionic polymers, leading to its precipitation. In this work was performed a detailed study on the stability of the properties of aqueous solutions and aqueous drilling fluids in the presence of sulphated and carboxylated polymers, using carboxymethylcellulose and kappa-carrageenan as polymer compounds carboxylated and sulfated model, respectively. The effects of ionic strength of the aqueous medium containing Na+, Mg2+ and Ca2+ on rheological properties of the polymer and drilling fluids solutions were evaluated by varying the concentration of salts, pH and temperature. It was observed that the fluids with κ-carrageenan suffered less influence against the contamination by the ions at pH 9 to 10, even at higher concentrations, but higher influence on pH> 11. The fluids containing carboxymethylcellulose were more sensitive to contamination, with rapid reduction in viscosity and significant increase of the filtrate volume, while the fluid based polymer sulfated kappa-carrageenan showed evidence of interaction with cations and preserve the rheological properties and improved stability the volume of filtrate.

Development of a Surface-Enhanced Raman Spectroscopy Method for the Detection of Benzodiazepines in Urine

Benzodiazepines are among the most prescribed compounds for anti-anxiety and are present in many toxicological screens. These drugs are also prominent in the commission of drug facilitated sexual assaults due their effects on the central nervous system. Due to their potency, a low dose of these compounds is often administered to victims; therefore, the target detection limit for these compounds in biological samples is 10 ng/mL. Currently these compounds are predominantly analyzed using immunoassay techniques; however more specific screening methods are needed. The goal of this dissertation was to develop a rapid, specific screening technique for benzodiazepines in urine samples utilizing surface-enhanced Raman spectroscopy (SERS), which has previously been shown be capable of to detect trace quantities of pharmaceutical compounds in aqueous solutions. Surface enhanced Raman spectroscopy has the advantage of overcoming the low sensitivity and fluorescence effects seen with conventional Raman spectroscopy. The spectra are obtained by applying an analyte onto a SERS-active metal substrate such as colloidal metal particles. SERS signals can be further increased with the addition of aggregate solutions. These agents cause the nanoparticles to amass and form hot-spots which increase the signal intensity. In this work, the colloidal particles are spherical gold nanoparticles in aqueous solution with an average size of approximately 30 nm. The optimum aggregating agent for the detection of benzodiazepines was determined to be 16.7 mM MgCl2, providing the highest signal intensities at the lowest drug concentrations with limits of detection between 0.5 and 127 ng/mL. A supported liquid extraction technique was utilized as a rapid clean extraction for benzodiazepines from urine at a pH of 5.0, allowing for clean extraction with limits of detection between 6 and 640 ng/mL. It was shown that at this pH other drugs that are prevalent in urine samples can be removed providing the selective detection of the benzodiazepine of interest. This technique has been shown to provide rapid (less than twenty minutes), sensitive, and specific detection of benzodiazepines at low concentrations in urine. It provides the forensic community with a sensitive and specific screening technique for the detection of benzodiazepines in drug facilitated assault cases.

Refractometry Studies of the Optical Properties of Polymer Films and the Development of Polymer Coated Refractive Index Sensors

Sensors for real-time monitoring of environmental contaminants are essential for protecting ecosystems and human health. Refractive index sensing is a non-selective technique that can be used to measure almost any analyte. Miniaturized refractive index sensors, such as silicon-on-insulator (SOI) microring resonators are one possible platform, but require coatings selective to the analytes of interest. A homemade prism refractometer is reported and used to characterize the interactions between polymer films and liquid or vapour-phase analytes. A camera was used to capture both Fresnel reflection and total internal reflection within the prism. For thin-films (d = 10 μm - 100 μm), interference fringes were also observed. Fourier analysis of the interferogram allowed for simultaneous extraction of the average refractive index and film thickness with accuracies of ∆n = 1-7 ×10-4 and ∆d < 3-5%. The refractive indices of 29 common organic solvents as well as aqueous solutions of sodium chloride, sucrose, ethylene glycol, glycerol, and dimethylsulfoxide were measured at λ = 1550 nm. These measurements will be useful for future calibrations of near-infrared refractive index sensors. A mathematical model is presented, where the concentration of analyte adsorbed in a film can be calculated from the refractive index and thickness changes during uptake. This model can be used with Fickian diffusion models to measure the diffusion coefficients through the bulk film and at the film-substrate interface. The diffusion of water and other organic solvents into SU-8 epoxy was explored using refractometry and the diffusion coefficient of water into SU-8 is presented. Exposure of soft baked SU-8 films to acetone, acetonitrile and methanol resulted in rapid delamination. The diffusion of volatile organic compound (VOC) vapours into polydimethylsiloxane and polydimethyl-co-polydiphenylsiloxane polymers was also studied using refractometry. Diffusion and partition coefficients are reported for several analytes. As a model system, polydimethyl-co-diphenylsiloxane films were coated onto SOI microring resonators. After the development of data acquisition software, coated devices were exposed to VOCs and the refractive index response was assessed. More studies with other polymers are required to test the viability of this platform for environmental sensing applications.

Study of DNA damage with a new system for irradiation of samples in a nuclear reactor

FAPESP:97/5550

Elettrodeposizione di catalizzatori a base di Rh su schiume e fibre metalliche di FeCrAlloy per la produzione di syngas

The preparation of structured catalysts active in the catalytic partial oxidation of methane to syngas, was performed by electrosynthesis of hydroxides on FeCrAlloy foams and fibers. Rh/Mg/Al hydrotalcite-type compounds were prepared by co-precipitation of metallic cations on the support and successive calcination. Electrochemical reactions have been studied during the electrodeposition by linear sweep voltammetry. The experiments were performed at supports immersed in KNO3, KCl, Mg2+ and Al3+ aqueous solutions, starting by different precursors (nitrate and chlorides salts) and modifying the Mg/A ratio. Rh/Mg/Al hydrotalcite-type compounds were deposited on metal foams by applying a -1.2V vs SCE potential for 2000s with a nitrate solution of 0.06M total metal concentration. Firstly it was studied the effect of Mg on the coating propierties, modifying the Rh/Mg/Al atomic ratio (5/70/25, 5/50/45, 5/25/70 e 5/0/95). Then the effect of the amount of Rh was later investigated in the sample with the largest Mg content (Rh/Mg/Al = 5/70/25 and 2/70/28).The results showed that magnesium allowed obtaining the most homogeneous and well adherent coatings, wherein rhodium was well dispersed. The sample with the Rh/Mg /Al ratio equal to5/70/25 showed the best catalytic performances. Decreasing the Rh content, the properties of the coating were not modified, but the catalytic activity was lower, due to a not enough number of active sites to convert the methane. The work on metal fibers focused on the effect of precursor concentration, keeping constant composition, potential and synthesis time at the values of Rh/Mg/Al =5/70/25, -1.2V vs SCE and 1000s. However fibers geometry did not allow to obtain a high quality coating, even if results were quite promising.