Sulfated Polyborate, a novel buffer for low pH mobile phase on a non-end capped stationary phase in reverse phase liquid chromatography

Background: Sulfated Polyborate, a novel inorganic material primarily designed as a catalyst, has shown properties such as high solubility in organic solvents, low U.V. cut-off, and pKa ≈2.0, which suggests its potential as a mobile phase buffer for reverse-phase liquid chromatography. Objective: This study aims to substantiate the role of Sulfated Polyborate as mobile phase buffer for reverse-phase liquid chromatographic analysis of basic drugs with high pKa values viz. Bisoprolol fumarate, Timolol maleate, Verapamil hydrochloride, and Carvedilol. Methods: Solubilities, U.V. cut-offs, and pKa of Sulfated Polyborate was first experimentally confirmed. The behaviour of Sulfated Polyborate as mobile phase buffer at pH 3.0 was ascertained by varying the buffer concentration, flow rates, and percent organic modifier for elution of the four basic drugs on a non-end capped octyl silyl (C8) column. Similarly, the study was performed with KH2PO4 as a reference buffer. The column performance and conductometric measurements ascertained the impact of Sulfated Polyborate on the stationary phase. Results: Sulfated Polyborate and KH2PO4 buffers showed correlation coefficients of 0.99 and 1.00 for analyte retention factors for variation of buffer concentration and organic modifier composition, respectively. Peak symmetries and the number of theoretical plates were improved from > 2.0 to < 2.0 and ≈1000 to ≈3000, respectively, for Variation in buffer concentrations. Similar Van Deemter plots indicated equivalency of Sulfated Polyborate and KH2PO4 buffers. The column performance and conductometric measurements depicted no adsorption on the stationary phase. Conclusion: The present study demonstrates Sulfated Polyborate as a novel buffer for analytes with higher pKa on reverse-phase liquid chromatography.

Effect of Organic Modifier Types on the Physical–Mechanical Properties and Overall Migration of Post-Consumer Polypropylene/Clay Nanocomposites for Food Packaging

The deterioration of the physical–mechanical properties and loss of the chemical safety of plastics after consumption are topics of concern for food packaging applications. Incorporating nanoclays is an alternative to improve the performance of recycled plastics. However, properties and overall migration from polymer/clay nanocomposites to food require to be evaluated case-by-case. This work aimed to investigate the effect of organic modifier types of clays on the structural, thermal and mechanical properties and the overall migration of nanocomposites based on 50/50 virgin and recycled post-consumer polypropylene blend (VPP/RPP) and organoclays for food packaging applications. The clay with the most hydrophobic organic modifier caused higher thermal stability of the nanocomposites and greater intercalation of polypropylene between clay mineral layers but increased the overall migration to a fatty food simulant. This migration value was higher from the 50/50 VPP/RPP film than from VPP. Nonetheless, clays reduced the migration and even more when the clay had greater hydrophilicity because of lower interactions between the nanocomposite and the fatty simulant. Conversely, nanocomposites and VPP/RPP control films exhibited low migration values in the acid and non-acid food simulants. Regarding tensile parameters, elongation at break values of PP film significantly increased with RPP addition, but the incorporation of organoclays reduced its ductility to values closer to the VPP.

Short alkyl chain length ionic liquid as organic modifier in polypropylene/clay nanocomposite: a thermal comparative study

The most common polymeric nanocomposites are constituted of organically-modified clays. Generally, these organic modifiers are based on quaternary ammonium salts. These systems have as disadvantage the low thermal resistance of its modifiers under processing. Ionic liquids (IL) with different molecular structures can be used as organic modifier in lamellar clays-based polymeric nanocomposites, being promising not only to increase interactions between the nanoclay and the matrix, but also to increase the thermal resistance. In this study, polypropylene-based/montmorillonite nanocomposites were compared from two different organic modifiers. The use of short alkyl chain length imidazolium-based IL as montmorillonite modifier was investigated in terms of the thermal stability when compared to the usual quaternary ammonium salt surfactant. Integral procedure decomposition temperature was employed to determine the effect of these two different organoclay modifiers in PP-nanocomposites. The activation energy for these samples was calculated using Flynn–Wall–Ozawa (FWO) method. It was also used the multiple linear regression analysis to calculate the activation energy in order to evaluate the accuracy of this method when applied to nanocomposites. Article Highlights Short length alkyl group in ionic liquid was able to improve the thermal stability of PP-based nanocomposite. IPDT methodology is more realistic to evaluate the thermal stability of ionic liquid-based nanocomposite. MLR methodology was efficient to assess the entropic contribution associated to polymer-clay interactions, inter-lamellae spaces and interface morphology.

Utilization of experimental design for the establishment and optimization of RP-HPLC method for the estimation of two selective serotonin reuptake inhibitors/benzodiazepines combinations in presence of their related compounds

Background: Design of experiment (DOE) is considered the most powerful tool to identify factors that affect variation and improve the response by tuning these factors. In the present work, DOE was applied to establish an innovative, sensitive and precise HPLC method for the simultaneous determination of Escitalopram oxalate, Paroxetine hydrochloride hemihydrate and Clonazepam in presence of their related compounds in drug substance and drug products. Methods: Buffer molarity, % organic modifier (acetonitrile content) at the beginning/end of gradient, flow rate at the beginning/end of gradient, pH of mobile phase and column temperature were screened using Plackett-Burman design (PBD) model. The main effect plot showed that % organic modifier at the beginning/end of gradient and flow rate at the beginning of gradient were statistically significant variables influencing peaks resolution (p<0.05). Box-Behnken design (BBD) was then used as optimization model in order to achieve the highest possible resolution with the least possible experimental trials through studying interaction and quadratic effects of these three factors. Finally, the optimum condition for predicated peak resolution could be achieved by desirability function. Results: After optimization, chromatographic separation was attained on Agilent Zorbax SB C18 (4.6×250mm, 5µm) column using gradient elution of mobile phase: (A) potassium dihydrogen phosphate (pH 2.7; 0.025M) and (B) acetonitrile at ambient column temperature with the last eluted compound at less than 17 min. The flow rate was maintained at 1/2.3 mLmin-1 with UV detection at 245/210 nm using time programming. Conclusion: The optimized chromatographic method was used for stability indicating assay of the cited drugs in presence of their related compounds according to ICH Q2R1 guidelines.

Development of HPLC Method for the Purity Test by Design of Experiments and Determination of Activation Energy of Hydrolytic Degradation Reactions of Sofosbuvir

Background: The present study was focused on the development of HPLC method for purity testing of sofosbuvir by the Design of Experiments and determination of the activation energy of hydrolytic degradation reactions of sofosbuvir using HPLC based on the kinetics of sofosbuvir degradation. Methods: Following four factors for the Design of Experiments were selected, stationary phase, an organic modifier of the mobile phase, column temperature and pH of the mobile phase. These factors were examined in two or three level experimental design using Modde 11.0 (Umetrics) software. The chromatographic parameters like resolution, USP tailing and discrimination factor were calculated and analysed by partial least squares. The chromatography was performed based on Design of Experiments results with the mobile phase containing ammonium phosphate buffer pH 2.5 and methanol as an organic modifier. Separation was achieved using gradient elution on XBridge BEH C8 at 50 °C and a flow rate of 0.8 mL/min. UV detection was performed at 220 nm. The activation energy of hydrolytic degradation reactions of sofosbuvir was evaluated using two different calculation methods. The first method is based on the slope of dependence of natural logarithm of the rate constant on inverted thermodynamic temperature and the second approach is the isoconversional method. Results and Conclusion: Calculated activation energies were 77.9 ± 1.1 kJ/mol for the first method and 79.5 ± 3.2 kJ/mol for the isoconversional method. The results can be considered to be identical, therefore both calculation methods are suitable for the determination of the activation energy of degradation reactions.