Determination of absorption curves, dissolution profiles and establishment of in vitro-in vivo correlation by in silico methods using GastroPlusTM and DDDPlusTM

The use of computer programs to predict drug absorption in humans and to simulate dissolution profiles has become a valuable tool in the pharmaceutical area. The objective of this study was to use in silico methods through software GastroPlusTM and DDDPlusTM to simulate drug absorption curves and dissolution profiles, and to establish in vitro-in vivo correlations (IVIVCs). The work presented herein is divided into five chapters and includes the drugs ketoprofen, pyrimethamine, metronidazole, fluconazole, carvedilol and doxazosin. In Chapter 1, simulated plasma curves for ketoprofen matrix tablets are presented and IVIVC was established. The use of simulated intrinsic dissolution tests for pyrimethamine and metronidazole as a tool for biopharmaceutics classification is detailed in Chapter 2. In Chapter 3, simulation of plasma curves for fluconazole capsules with different dissolution profiles is demonstrated as a tool for biowaiver. IVIVC studies were also conducted for carvedilol immediate-release tablets from dissolution profiles in Chapter 4. Chapter 5 covers the application of simulated dissolution tests for development of doxazosin extended-release formulations. Simulation of plasma curves and IVIVC using the software GastroPlusTM as well as intrinsic dissolution tests and dissolution profiles using the software DDDPlusTM proved to be a tool of wide application in predicting biopharmaceutical characteristics of drugs and formulations, allowing the reduction of time and costs of experimental laboratory work.

Spectrophotometric and potentiometric investigations of copper (II)-ethanolamine complexes - Part I. Monoethanolamine

Spectrophotometric and potentiometric investigations have been carried out on copper-monoethanolamine complexes. Job plots at 920, 760 and 620 mµ have indicated the formation of CuA++, CuA2/++ and CuA3 ++. The$$\bar n - pA$$ curves have been obtained by a slight modification of the method of corresponding solutions and by pH measurements. The$$\bar n$$ vs. pA curves obtained at different metal concentrations coincide indicating the formation of mononuclear complexes. Experiments conducted with 0·1. 0·2, 0·5 and 1·0 M monoethanolammonium ion indicate the formation of mononuclear hydroxy complexes above pH 6. The nature of E m vs pA curves is closely analogous to that of$$\bar n$$ vs. pA curves. Absorption spectra taken at pH 9·8 with different amounts of monoethanolamine has given evidence for the formation of (CuA3OH·A)+.$$\bar n - pA$$ curves have been analyzed and the values ofβ 1, 1,β 1, 2 andβ 1, 3 have been obtained. Curves showing the distribution of complexes and the absorption curves of the individual complexes (CuA++, CuA2/++, and CuA3/++) have been calculated.

Spectrophotometric and potentiometric investigations of copper (II)-Ethanolamine complexes - Part III. diethanolamine (Gaussian analysis of electronic spectra in mono and diethanolamine systems)

Spectrophotometric and potentiometric investigations have been carried out on copper-diethanolamine system. Job plots at 900, 900 and 580 mμ have indicated the formation of CuD++, CuD2++ and CuD3++. The n- pA curves obtained indicate the formation of CuD++, CuD2++, CuD3++, CuDOH+, CuD2OH+ and CuD3OH+. The n- pA curves have been analyzed to obtain the stability constants of these complexes. Absorption curves of pure complexes have been computed by a graphical method. Gaussian analysis of the absorption curves of pure and hydroxy complexes show the presence of a second band, indicating that the structure is that of a distorted octahedron.

Temperature characteristics of optical parameters of phthalocyanine LB films and spin-coated films

The LB films and spin-coated films of tetra-neopentoxy phthalocyanine zinc (TNPPcZn) were prepared and annealed at different temperatures. Their refractive index (n) and extinction coefficient (k) were measured by p-polarized reflectance. The similar value of n and k, as well as similar changing tendency of it and k at varied annealing temperatures, was found between LB films and spin-coated films. In addition, the absorption curves of TNPPcZn LB films and spin-coated films in visible range at different annealing temperature were investigated. The results indicate that the changing tendency of the extinction coefficient of two kinds of TNPPcZn films obtained from two methods mentioned above were coincident. When the annealing temperature increased to 150 degrees C, the monomers of TNPPcZn films transformed to aggregates, n(f) and k(f) of the films increased. Further, n(f) and k(f) decreased as aggregates changed back to monomers again at the annealing temperature of 300 degrees C. The experimental results coincide well with the theoretical analysis. (C) 2004 Elsevier B.V. All rights reserved.

非饱和膨胀土力学特性及其工程处置研究

The unsaturated expansive soil is a hotspot and difficulty in soil mechanics inland and outland. The expansive soil in our China is one of the widest in distributing and greatest in area, and the disaster of expansive soil happens continually as a result. The soil mechanics test, monitor, numerical simulation and engineering practice are used to research swell and shrinkage characteristic, edge strength characteristic and unsaturated strength characteristic of Mengzi expansive soil. The seep and stability of the slope for expansive soil associated with fissure are analyzed and two kinds of new technique are put forward to be used in expansive soil area, based on disaster mechnics proposed of the slope.The technique of reinforcement in road embankment is optimized also. Associated with engineering geology research of Mengzi expansive soil, mineral composition, chemical composition, specific area and cation content, dissolubility salt and agglutinate, microcosmic fabric characteristic, cause of formation and atmosphere effect depth are analyzed to explain the intrinsic cause and essence of swell and shrinkage for expansive soil. The rule between swell-shrinkage and initial state, namely initial water content, initial dry density and initial pressure, can be used to construction control. Does Response model is fit to simulate the rule, based on ternary regression analysis. It has great meaning to expansive soil engineering in area with salt or alkali. The mechanics under CD, CU and GCU of expansive soil is researched by edge surface theory to explain the remarkable effect of consolidation pressure, initial dry density, initial water content, cut velocity, drainage and reinforcement to the edge strength characteristic. The infirm hardening stress strain curves can be fitted with hyperbola model and the infirm softening curves can be fitted with exponential model. The normalization theory can be used to reveal the intrinsic unity of the otherness which is brought by different methods to the shear strength of the same kinds of samples. The unsaturated strain softening characteristic and strength envelope of remolding samples are researched by triaxial shear test based on suction controlled, the result of which is simulated by exponential function. The strength parameters of the unsaturated samples are obtained to be used in the unsaturated seep associated with rainfall. The elasticity and plasticity characters of expansive soil are researched to attain the model parameters by using modified G-A model. The humidification destroy characteristic of expansive soil is discussed to research the disaster mechanism of the slope with the back pressure increasing and suction decreasing under bias pressure consolidation. The indoor and outdoor SWCCs are measured to research the effect factors and the rule between different stress and filling environment. The moisture absorption curves can express the relationship between suction and water content in locale. The SWCCs of Mengzi expansive soil are measured by GDS stress path trixial system. The unsaturated infiltration function is gained to research seep and stability of the slope of expansive soil. The rainfall infiltration and ability of slope considering multifarious factors are studied by analyzing fissure cause of Mengzi expansive soil. The mechanism of the slope disaster is brought forward by the double controlling effect between suction and fissure. Two new kinds of technique are put forward to resolve disaster of expansive soil and the technique of reinforcement on embankment is optimized, which gives a useful help to solving engineering trouble.

Extração e exportação de nutrientes em cultivares de batata: II - micronutrientes

Cultivares de batata mais produtivas possivelmente exigem maior quantidade de micronutrientes, porém no Brasil há carência de informações sobre extração e exportação de micronutrientes pelas principais cultivares de batata utilizadas. O objetivo deste trabalho foi avaliar a produtividade de tubérculos, a extração e a exportação de micronutrientes nas cultivares de batata Ágata, Asterix, Atlantic, Markies e Mondial. O experimento foi conduzido durante a safra de inverno, em um Latossolo Vermelho, no município de Itaí (SP). As parcelas foram constituídas pelas cinco cultivares, e as subparcelas, por épocas de coletas, realizadas no momento do plantio e a cada sete dias após a emergência. As cultivares Mondial e Asterix, mais produtivas, apresentaram maior extração de micronutrientes, com quantidades médias por hectare de 71 g de B, 122 g de Cu, 2.228 g de Fe, 618 g de Mn e 405 g de Zn. As menores quantidades extraídas foram observadas na cultivar Atlantic, com valores de 50, 81, 1.960, 544 e 270 g ha-1 de B, Cu, Fe, Mn e Zn, respectivamente. A fase de maior demanda por B ocorre logo após o início da formação de tubérculos, aos 34 DAP, enquanto a maior demanda por Fe e Mn inicia-se a partir dos 42 DAP e vai até 63 DAP. O Cu e o Zn são absorvidos em maiores proporções a partir dos 64 DAP até o final do ciclo. A quantidade de B, Cu, Mn e Zn exportada foi dependente da cultivar, com valores por hectare variando de 48 a 22 g de B, 79 a 16 g de Cu, 65 a 37 g de Mn e 167 a 83 g de Zn. A quantidade de Fe exportada não variou entre as cultivares, sendo, em média, de 243 g ha-1. A quantidade de micronutrientes extraída e exportada pela batateira variou com as cultivares utilizadas, indicando necessidade de manejo diferencial da adubação.

Extração e exportação de nutrientes em cultivares de batata: I - macronutrientes

A determinação das quantidades de nutrientes absorvidas durante o ciclo de desenvolvimento é de suma importância para estabelecer as épocas em que esses elementos são mais exigidos e as quantidades corretas que devem ser disponibilizadas à cultura da batata. No entanto, quase não existem essas informações para as principais cultivares utilizadas no Brasil. O objetivo deste trabalho foi avaliar a extração e a exportação de macronutrientes pelas cultivares de batata Ágata, Asterix, Atlantic, Markies e Mondial. O experimento foi conduzido durante a safra de inverno, em um Latossolo Vermelho, no município de Itaí (SP). As parcelas foram constituídas pelas cinco cultivares, e as subparcelas, por épocas de coletas, realizadas no momento do plantio e a cada sete dias após a emergência. As cultivares Mondial e Asterix, mais produtivas, apresentaram maior extração de macronutrientes, com quantidades médias por hectare de 116 kg de N, 18 kg de P, 243 kg de K, 50 kg de Ca e 13 kg de Mg, enquanto as cultivares Ágata, Atlantic e Markies extraíram menor quantidade, com valores médios de 92, 14, 178, 35 e 9 kg ha-1, respectivamente. A maior demanda por macronutrientes pelas cultivares estudadas ocorreu na fase inicial de enchimento dos tubérculos (42 a 70 DAP). A exportação de macronutrientes não esteve diretamente relacionada com a produtividade de tubérculos, já que a cultivar mais produtiva (Mondial) não foi a que exportou a maior quantidade de macronutrientes. A cultivar Asterix exportou maior quantidade de N, P, K e Mg, com valores de 88, 15, 220 e 8 kg ha-1, respectivamente, enquanto a menor exportação foi observada na cultivar Atlantic, com 48 kg ha-1 de N, 10 kg ha-1 de P, 143 kg ha-1 de K e 5 kg ha-1 de Mg. A variação entre as cultivares na extração, especialmente de K e N, indica necessidade de manejo diferencial da adubação.

Extração e exportação de nutrientes pelo híbrido de mamona Savana: I – macronutrientes

Low height castor bean hybrids and highly productive possibly need larger quantity of macronutients during its development cycle. However, in Brazil there is little information on extraction and exportation of macronutrients by low height castor bean hybrids, as on season as out-of-season growing. This study aimed to evaluate the nutrients extraction and exportation by Savana hybrid castor bean on season and out-of-season growing. The experiments were conducted during the season of 2005/2006 and out-of-season of 2006 in an Oxisol. The experimental design was a randomized block with four replications. The plots were consisted by harvest times of plants, which were composed by six plant rows to 5 m, spaced 0.45 m between rows. Samples were collected at 17, 31, 45, 59, 73, 97 and 120 days after emergence (DAE) during the season and at 17, 31, 45, 59, 80; 100 and 120 DAE in the out-of-season. The nutrients accumulation by Savana hybrid was small until the flowering (30 DAE), but intensified after this period. The period of greatest nutrient absorption occurred at 65 and 90 DAE for N, 70 and 80 DAE for P, 60 DAE for K and Mg, 55 and 60 DAE for Ca and S. The amounts absorbed per hectare by hybrid Savana ranged 155 to 31 kg of N, 17 to 3 kg of P, 71 to 13 kg of K, 56 to 12 kg of Ca, 28 to 4 kg of Mg and 29,5 to 7 kg of S in season and out-of-season, respectively. The yield was higher in growing season, but the nutrients extraction and exportation per ton of grain were similar among the seasons. Among 40% and 50% of N and S and most part of Mg, K and Ca accumulated in the plants returned to soil with crop residues, but less than 35% of P remained in the residues.

Extração e exportação de nutrientes pelo híbrido de mamona Savana: II – micronutrientes

Information about micronutrients extraction and exportation by castor bean hybrids of short stature, and the periods of highest demand for each micronutrient, are most importance for correct management to fertilization. This study aimed to evaluate the micronutrients extraction and exportation by Savana hybrid castor bean, on season and out-of-season growing. The experiments were conducted during season of 2005/2006 and out-of-season of 2006 in an Oxisol. The experimental design was a randomized block with four replications. The plots were consisted by harvest times of plants, which were carried out at 17, 31, 45, 59, 73, 97 and 120 days after emergence (DAE) during the season and at 17, 31, 45, 59, 80; 100 and 120 DAE in the out-of-season. In both seasons the order of micronutrients extraction by hybrid Savanna is: Fe> Mn> Zn> B> Cu> Mo, but with larger amounts of season cultivation. The time of greatest Zn and Mo absorption during the season and the Fe in out-of-season occurs at 80 DAE, although the other micronutrients are absorbed at higher rates between 50 and 65 DAE. In season the yield, nutrients extraction and exportation from soil are higher than out-of-season, but the nutrients extraction and exportation per ton show less variation between growing seasons. Fifty percent of zinc and 60% of Cu uptaken, on average, in out-of-season is exported with grains, but for the other micronutrients the proportion exported with grains is less than 40%.

Avaliação e modelagem da absorção de H2S do gás natural em coluna de leito estagnado

Natural gas, although basically composed by light hydrocarbons, also presents contaminant gases in its composition, such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). The H2S, which commonly occurs in oil and gas exploration and production activities, causes damages in oil and natural gas pipelines. Consequently, the removal of hydrogen sulfide gas will result in an important reduction in operating costs. Also, it is essential to consider the better quality of the oil to be processed in the refinery, thus resulting in benefits in economic, environmental and social areas. All this facts demonstrate the need for the development and improvement in hydrogen sulfide scavengers. Currently, the oil industry uses several processes for hydrogen sulfide removal from natural gas. However, these processes produce amine derivatives which can cause damage in distillation towers, can cause clogging of pipelines by formation of insoluble precipitates, and also produce residues with great environmental impact. Therefore, it is of great importance the obtaining of a stable system, in inorganic or organic reaction media, able to remove hydrogen sulfide without formation of by-products that can affect the quality and cost of natural gas processing, transport, and distribution steps. Seeking the study, evaluation and modeling of mass transfer and kinetics of hydrogen removal, in this study it was used an absorption column packed with Raschig rings, where the natural gas, with H2S as contaminant, passed through an aqueous solution of inorganic compounds as stagnant liquid, being this contaminant gas absorbed by the liquid phase. This absorption column was coupled with a H2S detection system, with interface with a computer. The data and the model equations were solved by the least squares method, modified by Levemberg-Marquardt. In this study, in addition to the water, it were used the following solutions: sodium hydroxide, potassium permanganate, ferric chloride, copper sulfate, zinc chloride, potassium chromate, and manganese sulfate, all at low concentrations (»10 ppm). These solutions were used looking for the evaluation of the interference between absorption physical and chemical parameters, or even to get a better mass transfer coefficient, as in mixing reactors and absorption columns operating in counterflow. In this context, the evaluation of H2S removal arises as a valuable procedure for the treatment of natural gas and destination of process by-products. The study of the obtained absorption curves makes possible to determine the mass transfer predominant stage in the involved processes, the mass transfer volumetric coefficients, and the equilibrium concentrations. It was also performed a kinetic study. The obtained results showed that the H2S removal kinetics is greater for NaOH. Considering that the study was performed at low concentrations of chemical reagents, it was possible to check the effect of secondary reactions in the other chemicals, especially in the case of KMnO4, which shows that your by-product, MnO2, acts in H2S absorption process. In addition, CuSO4 and FeCl3 also demonstrated to have good efficiency in H2S removal

Extração e exportação de nutrientes em cultivares de feijoeiro, sob níveis de adubação: I - Macronutrientes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Extração e exportação de nutrientes em cultivares de feijoeiro, sob níveis de adubação: II - Micronutrientes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Produtividade e qualidade de frutos de melão pele de sapo em função de diferente níveis de irrigação e adubações nitrogenada e potássica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Vibrational spectroscopic monitoring of CO2-O energy transfer: cooling processes in atmospheres of Venus & Mars

The vibrational excitation of CO2 by a fast-moving O atom followed by infrared emission from the vibrationally excited CO2 has been shown to be an important cooling mechanism in the upper atmospheresof Venus, Earth and Mars. We are trying to determine more precisely the efficiency (rate coefficient) of the CO2-O vibrational energy transfer. For experimental ease the reverse reaction is used, i.e. collision of a vibrationally excited CO2 with atomic O, where we are able to convert to the atmospherically relevant reaction via a known equilibrium constant. The goal of this experiment was to measure the magnitudes of rate coefficients for vibrational energy states above the first excited state, a bending mode in CO2. An isotope of CO2, 13CO2, was used for experimental ease. The rate coefficients for given vibrational energy transfers in 13CO2 are not significantly different from 12CO2 at this level of precision. A slow-flowing gas mixture was flowed through a reaction cell: 13CO2 (vibrational specie of interest), O3(atomic O source), and Ar (bath gas). Transient diode laser absorption spectroscopy was used to monitor thechanging absorption of certain vibrational modes of 13CO2 after a UV pulse from a Nd:YAG laser was fired. Ozone absorbed the UV pulse in a process which vibrationally excited 13CO2 and liberated atomic O.Transient absorption signals were obtained by tuning the diode laser frequency to an appropriate ν3 transition and monitoring the population as a function of time following the Nd:YAG pulse. Transient absorption curves were obtained for various O atom concentrations to determine the rate coefficient of interest. Therotational states of the transitions used for detection were difficult to identify, though their short reequilibration timescale made the identification irrelevant for vibrational energy transfer measurements. The rate coefficient for quenching of the (1000) state was found to be (4 ± 8) x 10-12 cm3 s-1 which is the same order of magnitude as the lowest-energy bend-excited mode: (1.8 ± 0.3) x 10-12 cm3 s-1. More data is necessary before it can be certain that the numerical difference between the two is real.

Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.