Estudio de la emisión acústica generada por deformación en tubos, sus fuentes y características

En el presente Trabajo de Tesis, se diseñó e implementó un sistema experimental para estudiar la Emisión Acústica (EA) producida durante la deformación triaxial de probetas en forma de aros. Se construyeron todos los componentes necesarios para los ensayos. Se diseñaron y construyeron distintos tipos de probetas, cortadas transversalmente de tubos de acero microaleado sin costura, usados en la industria petrolera, a fin de inducir distintas fuentes de EA (deformación, creación y propagación de fisuras, rotura de la capa de óxido). Se caracterizaron química, mecánica y metalográficamente los materiales de las probetas ensayadas. Las superficies de rotura de los materiales empleados, fueron observadas en un microscopio electrónico de barrido (MEB), identificándose los distintos tipos de fractura. Se realizaron 22 ensayos, sirviendo los 10 primeros, para poner a punto todo el sistema de medición, eligiéndose los parámetros óptimos. Se logró caracterizar cada tipo de probeta por el comportamiento medio de los parámetros Amplitud, Duración y Risetime de las señales de EA, obteniéndose una clara separación en "clusters". Esto permitiría en ensayos en campo sobre tubos similares, hacer una identificación general de las posibles fuentes de EA. No se encontró un comportamiento temporal definido en la evolución de los parámetros de las señales de EA, a medida que avanzaba cada ensayo. Estadísticamente se demostró que dentro de cada tipo de probeta, los ensayos son réplicas entre sí. Se calcularon los coeficientes de correlación entre los tres parámetros de las señales de EA, para todos los ensayos, encontrándose la mayor correlación entre la Amplitud y la Duración. Para cada ensayo, se estudiaron estadísticamente las distribuciones de los parámetros Duración, Risetime y Amplitud. No encontrándose una única función de distribución que ajustase todos los histogramas experimentales de los dos primeros. En el caso de la Amplitud, primero, de acuerdo a la ley potencial, se obtuvieron valores del exponente comprendidos entre los citados en la literatura publicada. Luego, se encontró que una única función de distribución ajustaba todos los histogramas experimentales, dicha función fue la Log-normal, que ya aparecía citada en la literatura publicada. Buscando alguna explicación física al hecho anterior, se analizó primero la influencia del sistema de detección, demostrándose que el transductor piezoeléctrico de banda ancha empleado para recoger la EA producida, mantiene la linealidad entre la amplitud de los impulsos mecánicos incidentes en el sensor (deformación de la superficie del material) y la amplitud de las señales eléctricas salientes (Amplitud de las señales de EA). Luego, se demostró, teniendo en cuenta el comportamiento estadístico de los fenómenos físicos involucrados, que las amplitudes de las deformaciones dentro del material obedecen a una distribución Log-normal. Teniendo en cuenta la linealidad del sistema de registro de la EA, se concluyó que las Amplitudes de las señales de EA deben seguir la misma distribución Log-normal. Por último, se hacen algunos comentarios destinados a relacionar dos fenómenos que aunque ocurren a escalas muy diferentes, parecen responder a la misma dinámica, la E A a escala microscópica, y los terremotos a escala varios ordenes de magnitud mayor. Finalmente, se sugiere para estudios posteriores, la aplicación de los nuevos conceptos como criticalidad auto-organizada, fractales y ruido 1/f al fenómeno de la Emisión Acústica.Fil:López Pumarega, María Isabel. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina

Feasibility of the estimation of octanol-water distribution coefficients of acidic drugs by microemulsion electrokinetic chromatography

Previous studies have shown that a microemulsion electrokinetic chromatography (MEEKC) system can estimate the logarithm of the octanol-water partition coefficient (log Po/w) of neutral solutes. In the present work, the applicability of the method to partially and fully ionized acids has been evaluated. Naproxen, a monoprotic acid, has been used as test solute. The retention factor (k) of this compound has been measured in MEEKC at several values of pH and the retention factor-pH profile has been established. As log Po/w correlates with log kMEEKC for neutral compounds, this correlation has been used to estimate the logarithm of the octanol-water partition coefficient of the neutral (log Po/w(HA)), and the fully ionized (log P o/w(A-)) forms of naproxen. Then, the logarithm of the octanol-water distribution coefficient (log Do/w) of the partially ionized form of the acid has been estimated. The comparison of the estimated values with the ones obtained experimentally using the classical procedures, such as the shake-flask method, shows differences under 0.4 log Do/w units either if the acid is partially ionized or in its neutral form in the most part of the pH range. However, the method overestimates the log Do/w of the highly (>99.5 %) or fully ionized form of naproxe

Determination of the retention factor of ionizable compounds in microemulsion electrokinetic chromatography

Determination of the retention factor of ionized compounds in microemulsion electrokinetic chromatography requires two mobility measurements at the same pH: one in the presence of the microemulsion and another in plain buffer. However, it has been observed that in some cases subtracting one mobility from another determined in a different medium leads to negative retention factors, which makes no sense from a chemical point of view. This indicates that there is some error in the process which has a direct impact when retention factors are used for further applications. Here, we evaluate how the components of the microemulsion confer different properties to the buffer medium, particularly varying the viscosity parameter (which is inversely related to mobility). Whereas sodium dodecyl sulfate, the surfactant used in the microemulsion, has little effect on the medium viscosity (only an increase of 5%-6%), the presence of 1-butanol, used as a stabilizer, increases it by around 30%. Meanwhile, heptane, which is used as an oil, provokes a slight decrease. Consequently, the mobilities obtained in the microemulsion system are shifted to higher values (less negative mobilities) compared to mobilities obtained in the aqueous buffer, and so one cannot be directly subtracted from the other. Since the microemulsion-buffer medium cannot be directly reproduced, we propose a correction that takes into account the variation of viscosities. This is determined from the electrophoretic mobility of the benzoate ion. As this ion does not interact with the microemulsion, the ratio of its mobilities (measured in plain buffer and microemulsion) is equivalent to the ratio of viscosities, and can be used as the correction factor for other measurements. Thus, mobilities in buffer and microemulsion media are placed on the same scale, overcoming the errors in retention factor determination

Tadpole toxicity prediction using chromatographic systems

Toxicity has been emulated in tadpole species through chromatographic systems. The parameter studied to evaluate the non-specific toxicity of a compound is the narcosis concentration (Cnar), which is defined as the concentration needed for the immobilization of the organism. Because experimental investigation with animals is lengthy, costly, technically difficult, and ethically questionable, there is a great interest in developing surrogate physicochemical systems able to emulate biological systems to obtain the same information in a faster, more economic, and easier manner. In order to see which chromatographic systems would be able to emulate tadpole narcosis, both, tadpole narcosis data and data in several chromatographic and electrophoretic systems, were fitted to a linear solvation energy relationship (LSER) model. Thus, by comparison of the models it was possible to see which of the chromatographic systems were more similar to the biological one. The physicochemical systems that best emulate tadpole narcosis were an HPLC system based on an immobilized artificial membrane (IAM) column, and two micellar electrokinetic chromatography (MEKC) systems based on sodium taurocholate (STC) and a mixture of sodium dodecylsulphate (SDS) and Brij 35 as surfactants. A system based on a RP18 HPLC column also was selected for comparison because it is a common column in most analytical laboratories. To establish the models, a set of compounds with known Cnar values were analyzed in the chromatographic, and electrophoretic selected systems and, then, the retention factor (k) was correlated to the concentration of narcosis. Statistics showed that the system based on STC micelles was the best to emulate toxicity in tadpoles. The robustness and predictive ability of the developed models were validated

Estimation of the octanol-water distribution coefficient of acidic compounds by microemulsion electrokinetic chromatography

The feasibility of extending the determination of the lipophilicity of partially ionized acids (log Do/w) by microemulsion electrokinetic chromatography (MEEKC) is tested. Theoretical considerations predict that a linear log Do/w vs. log k correlation can be obtained only when the neutral and ionic forms of an acid follow the same correlation equation and the slope of the correlation is unity. In practice, since the lipophilicity of the neutral acid is much higher than that of the ionic form and the correlation slope is not very different from 1, the general linear correlation for neutral compounds can be applied across most of the ionization range of the acid. The linear correlation between log Po/w and log k of 20 neutral solutes (calibration curve) has been established and extended to 6 acids used as models, tested across their full ionization range. log Do/w-pH, and log k-pH profiles have been obtained for these 6 acids, and plotted log Do/w against log k for any acid at any degree of ionization. Furthermore, the log Do/w of the acids has been estimated from the calibration curve and log k-pH profile, and compared to values in the literature determined using reference methods such as the shake-flask one. Accurate values have been obtained using the MEEKC method when the acids are in their neutral form or partially ionized (ionization degree, α < 0.995). However, this parameter is overestimated when the acids are highly or fully ionized (α ≈ 1). Finally, in order to test the applicability of this method, we have applied the same procedure to estimate log Do/w at pH = 7.4 (blood physiological pH) of a set of 30 additional compounds (including partially and fully ionized acids). The results at this pH foll

Estimation of the octanol-water distribution coefficient of basic compounds by a cationic microemulsion electrokinetic chromatography system

The octanol-water partition coefficient (Po/w), or the octanol-water distribution coefficient (Do/w) for ionized compounds, is a key parameter in the drug development process. In a previous work, this parameter was estimated through the retention factor measurements in a sodium dodecyl sulfate (SDS) - microemulsion electrokinetic chromatography (MEEKC) system for acidic compounds. Nonetheless, when ionized basic compounds were analyzed, undesirable ion pairs were formed with the anionic surfactant and avoided a good estimation of log Do/w. For this reason, an alternative MEEKC system based on a cationic surfactant has been evaluated to estimate Po/w or Do/w of neutral compounds and ionized bases. To this end, it has been characterized through the solvation parameter model (SPM) and compared to the octanol-water partition system. Results pointed out that both systems show a similar partition behavior. Hence, the log Po/w of a set of neutral compounds has been successfully correlated against the logarithm of the retention factor (log k) determined in this MEEKC system. Then, the log Do/w of 6 model bases have been estimated at different pH values and they have been compared to data from the literature, determined by the reference shake-flask and potentiometric methods. Good agreement has been observed between the literature and the estimated values when the base is neutral or partially ionized (up to 99 % of ionization)

Modeling aquatic toxicity through chromatographic systems

Environmental risk assessment requires information about the toxicity of the growing number of chemical products coming from different origins that can contaminate water and become toxicants to aquatic species or other living beings via the trophic chain. Direct toxicity measurements using sensitive aquatic species can be carried out but they may become expensive and ethically questionable. Literature refers to the use of chromatographic measurements that correlate to the toxic effect of a compound over a specific aquatic species as an alternative to get toxicity information. In this work, we have studied the similarity in the response of the toxicity to different species and we have selected eight representative aquatic species (including tadpoles, fish, water fleas, protozoan, and bacteria) with known nonspecific toxicity to chemical substances. Next, we have selected four chromatographic systems offering good perspectives for surrogation of the eight selected aquatic systems, and thus prediction of toxicity from the chromatographic measurement. Then toxicity has been correlated to the chromatographic retention factor. Satisfactory correlation results have been obtained to emulate toxicity in five of the selected aquatic species through some of the chromatographic systems. Other aquatic species with similar characteristics to these five representative ones could also be emulated by using the same chromatographic systems. The final aim of this study is to model chemical products toxicity to aquatic species by means of chromatographic systems to reduce in vivo testing