Development of a CZE Method for the Determination of Olmesartan Medoxomil in Tablets

A CZE method was developed and validated for the analysis of Olmesartan medoxomil (OLMD) in tablets. The influences of pH, buffer concentration, applied voltage and capillary temperature on the migration time of OLMD were investigated. About 50 mM pH 6.5 phosphate buffer were used as background electrolyte. The optimum instrument parameters were found to be 30 °C temperature with 30 kV applied voltage and diode array detection was carried out at 210 nm. OLMD was hydrodynamically injected (P _inj  = 50 mbar, t _inj  = 3 s) and an internal standard, diflunisal (IS), was used to improve the precision and repeatability. Under these conditions, the migration time of OLMD was 2.32 min and the total analysis time was shorter than 5 min. Linearity range for the developed method was found to be 2.0–50.0 μg mL^?1 and the limit of detection was 0.5 μg mL^?1. The developed method was applied for the analysis of OLMD in pharmaceutical tablet formulations.     

Modeling of asymmetric membrane formation by dry-casting method

Many polymeric membranes are produced by phase inversion technique invented by Loeb and Sourirajan in 1962. The dry-casting method is one of the major phase inversion techniques in which a homogeneous polymer solution consisting of solvent(s) and nonsolvent(s) is cast on a support and then evaporation of the casting solution takes place under convective conditions. In this paper, we model membrane formation by the dry-casting method. The model takes into account film shrinkage, evaporative cooling, coupled heat, and mass transfer and incorporates practical and reliable diffusion theory as well as complex boundary conditions especially at the polymer solution/air interface. The predictions from the model provide composition paths, temperature, and thickness of the solution. By plotting the composition paths on the ternary phase diagram, we ascertain the general structural characteristics of the membranes prepared from particular casting conditions. The predictive ability of the model was evaluated by comparing the results with the experimental data obtained from gravimetric measurements for cellulose acetate (CA)–acetone–water system. In an attempt to illustrate the importance of diffusion formalism on the predictions, recently proposed multicomponent diffusion theory and its simplified forms were utilized in the model. The computational results show that the critical factor for capturing the accurate behavior of membrane formation is the diffusion formalism utilized in the model.     

Measurement of ternary polymer/solvent equilibrium data by vapor-phase infrared spectroscopy

Vapor–liquid equilibrium (VLE) data for binary toluene/PVAC, methanol/PVAC and ternary toluene/methanol/PVAC systems have been measured at 100 °C by using vapor-phase infrared spectroscopy. Binary data have been compared with literature data measured by different experimental techniques and agreement between our measurements and others was found to be good. The ternary VLE data indicate that the solubility of methanol in PVAC is not influenced by the presence of toluene, while the solubility of toluene is lowered due to presence of methanol. To predict ternary VLE data, the Entropic free volume and Kannan free volume models and the Flory-Huggins theory were used. The predictive abilities of Flory-Huggins theory and the Kannan free volume model are similar and better than that of the Entropic free volume model.     

A reversed-phase high-performance liquid chromatographic method for the determination of zafirlukast in pharmaceutical formulations and human plasma

Zafirlukast (ZAF) is a leukotriene receptor antagonist used in the treatment of chronic asthma. In this study, a simple and sensitive reversed-phase, high-performance liquid chromatographic method was developed for the determination of ZAF in pharmaceutical formulations and human plasma. Piribedil was used as an internal standard. Analysis was carried out on a Nucleosil C18 100 A (150 mm x 4.6 mm id, 5 Vm) column with acetonitrile-pH 3.0 acetate buffer (70 + 30, v/v) as the mobile phase at a flow rate of 0.8 mL/min. The peak was detected by an ultraviolet detector set at a wavelength of 240 nm. The retention times were about 3.9 min for piribedil and 5.8 min for ZAF. The developed method was applied to the determination of ZAF in its pharmaceutical formulation and spiked human plasma. For quantification of ZAF in spiked plasma, proteins were precipitated with ethanol before chromatographic analysis. The calibration range was linear from 49.69-437.50 ng/mL in spiked plasma. The absolute recovery from spiked plasma was 98.73 +/- 0.42% at a concentration of 254.78 ng/mL of ZAF. No endogenous substances from plasma were found to interfere.     

Solubility and diffusivity of methylmethacrylate and butylacrylate monomers in a MMA–BA copolymer

Mutual diffusion coefficients and sorption isotherms of methyl methacrylate (MMA) and butyl acrylate (BA) monomers in methyl methacrylate‐butyl acrylate copolymer (MMA‐BA) have been measured by gravimetric sorption. MMA is found to have higher solubility and diffusion rates in the copolymer than BA. Sorption data for MMA were interpreted using classical Flory‐Huggins thermodynamic theory with a constant interaction parameter (χ). A modified version of this theory has been applied to correlate the sorption data of BA, which exhibit a temperature and concentration‐dependent χ parameter. For MMA, the isotherm data reveal enhanced polymer‐solvent interactions with increasing temperature, while for BA the data indicate a drive toward phase separation with increasing temperature. Despite the difference in thermodynamic behavior, both monomers are found to exhibit Fickian diffusion and the diffusivity data are correlated reasonably well with the Vrentas‐Duda free volume theory. Some deviation between the free‐volume correlation and the experimental data is observed at the lowest temperature and BA concentration examined. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1996–2006, 2007     

Onsager consistency checks for multicomponent diffusion models

The Onsager reciprocity relations are applied to several recently proposed multicomponent diffusion models in an attempt to gauge their validity and ascertain their applicability. Each of these friction‐based diffusion models stems from the more general Bearman formalism through various assumptions regarding the individual friction coefficients. By assessing the compliance of the Bearman model with respect to the Onsager relations, we ascertain the validity of the simplifications introduced to each diffusion model and suggest which postulates lead to results consistent with the Onsager relations. Although some models are not consistent with the Onsager relations, each model predicts the multicomponent drying of polymer films reasonably well. The necessity for consistency with the Onsager development is, therefore, revisited. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1496–1504, 2001     

Crystallization of poly(vinyl alcohol) during solvent removal: Infrared characterization and mathematical modeling

Crystallization of semicrystalline polymer films during drying has a significant effect on the rate of solvent removal. Understanding and controlling the crystallization kinetics is important in controlling residual solvent levels and drying kinetics. The degree of crystallinity of the poly(vinyl alcohol) films during multicomponent drying was investigated using Fourier transform infrared spectroscopy (FTIR). The 1141 cm^?1 band is sensitive to the degree of crystallinity of the polymer and the growth of intensity of this band was monitored as drying progressed. The results from the FTIR studies were comparable to the results obtained from differential scanning calorimetry. Studies were conducted to test the effect of initial solvent composition (water–methanol mixture), drying temperature, and polymer molecular weight on the rate of crystallization and the final crystallinity of the films. An increase in initial methanol composition increased the crystallization rate but did not affect the final degree of crystallinity. An increase in drying temperature and decrease in polymer molecular weight increased the rate of crystallization as well as the final degree of crystallinity. Based on the experimental data, rate constants for crystallization kinetics were extracted from our previously developed model based on free volume theory. The experimental data and the simulation results showed good agreement. The ability of the free volume theory to illustrate the crystallization behavior validated the model and improved its capability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 930–935, 2007     

Oxidative polymerization of acrylamide in the presence of thioglycolic acid

Chemical polymerization of acrylamide at room temperature was examined by using thioglycolic acid-cerium (IV) sulfate and thioglycolic acid-KMnO₄ redox systems in acid aqueous medium. Water soluble polyacrylamides containing thioglycolic acid end groups were synthesized. The effects of the molar ratio of acrylamide to Ce(IV) n _AAm /n _Ce(IV) , the polymerization time, the temperature, the monomer concentration, the molar ratio of cerium (IV) sulfate to thioglycolic acid and the concentration of sulfuric acid on the yield and molecular weight of polymer were investigated. Lower molar ratios of acrylamide/Ce(IV) at constant monomer concentration resulted in an increase in the yield but a decrease in molecular weight of polymer. The increase of reaction temperature from 20 to 70°C resulted in a decrease in the yield but generally resulted in a constant value for the molecular weight of polymer. With increasing polymerization time, the yield and molecular weight of polymer did not change substantially. Ce(IV) and Mn(VII) ions are reduced to Ce(III) and Mn(II) ions respectively in the polymerization reaction. The existence of Ce(III) ion bound to polymer was investigated by UV-visible spectrophotometry and fluoresce measurements. The amount of Mn(II) incorporated into the polymer was determined using graphite furnace atomic absorption spectrometry. The mechanism of this phenomenon is discussed.     

Method for obtaining the rate coefficient of a second-order gas evolving reaction

The method is based on the measurement of pressures produced by collection of the gas during equal time intervals. It was applied to HCOOH decomposition in H₂SO₄.     

Understanding the effect of skin formation on the removal of solvents from semicrystalline polymers

The effect of glassy skin formation on the drying of semicrystalline polymers was investigated with a comprehensive mathematical model developed for multicomponent systems. Polymers with high glass‐transition temperatures can become rubbery at room temperature under the influence of solvents. As the solvents are removed from the polymer, a glassy skin can form and continue to develop. The model takes into account the effects of diffusion‐induced polymer crystallization as well as glassy–rubbery transitions on the overall solvent content and polymer crystallinity. A Vrentas–Duda free‐volume‐based diffusion scheme and crystallization kinetics were used in our model. The polymer–solvent system chosen was a poly(vinyl alcohol) (PVA)–water–methanol system. The drying kinetics of PVA films were obtained by gravimetric methods with swollen films with known water/methanol concentrations. The overall drying behaviors of the polymer system determined by our model and experimental methods were compared and found to match well. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3191–3204, 2005