Green electrochemical and chromatographic quantifications of the extremolyte ectoine in halophilic bacterial cultures and related pharmaceutical preparations.

The realistic implementation of electrochemistry into bacterial biosynthesis monitoring programs has always been a challenging task. In this study, two simple, rapid, selective, and sensitive potentiometric sensors were developed and optimized for quantitative analysis of the extremolyte / osmoprotector ectoine (ECT) in halophilic bacterial cultures and also in its related pharmaceutical products. The developed sensors were a Polyvinyl chloride membrane sensor (ECT-PVC) and a coated graphite sensor (ECT-CG). They were established based on the ion association complex of ectoine cation with phosphotungstic acid (ECT-PTA) counter anion as ion exchange site using dioctyl-phthalate (DOP) as a solvent mediator or plasticizer. The sensors exhibited fast, stable, selective, and linear Nernstian responses over a broad range of concentrations ranging from 1 × 10-5 to 1 × 10-2 M of the studied drug. The developed sensors were optimized and cross-validated with a proposed HPLC method according to ICH guidelines. The proposed methods were successfully employed to quantify the studied drug in three different types of halophilic bacterial cultures and in an ectoine nasal spray pharmaceutical product. The selected bacteria species were Chromohalobacter salexigens, Halobacillus halophilus, and Halomonas elongata. The proposed methods were statistically compared with the reported methods, demonstrating no significant difference with respect to accuracy and precision. Greenness and environmental impact were also evaluated for the proposed procedures, verifying that they were excellent green and eco-friendly analytical methods.

Eco-friendly multivariate curve resolution-alternating least squares and chromatographic quantifications of some veterinary drug residues in pharmaceutical industrial wastewater.

Three eco-friendly and cost-effective analytical methods were developed and optimized for quantitative analysis of some veterinary drug residues in production wastewater samples. The studied drugs were ivermectin, rafoxanide and sulfadimidine. A solid-phase extraction procedure was employed using Bond Elut C18 cartridges, prior to analysis. The first method was a chemometric approach called multivariate curve resolution - alternating least squares (MCR-ALS). A calibration model was developed and several figures of merit (RMSEP, SEP, bias, RE%) were calculated. The second method was a thin layer chromatography followed by densitometric measurements at 245 nm. The separation was performed using silica gel 60 F254 plates and ethyl acetate : acetonitrile : toluene : ammonia (20 : 3 : 2 : 1, by volume) as a developing system. The third method was a high performance liquid chromatographic separation on HiQsil C18 HS column with UV detection at 245 nm. The mobile phase consisted of acetonitrile : methanol : water (60 : 25 : 15, by volume), with a flow rate of 1.5 mL min-1. The proposed methods were validated according to ICH guidelines. The described procedures were applied to quantify the studied drug residues in synthetic and real industrial wastewater samples. The proposed methods were statistically compared with the official and the reported methods, showing no significant difference with respect to accuracy and precision at P = 0.05.