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Chronic pain is extremely prevalent among patients with cancer. From the clinical experience, usually, an adjuvant analgesic such as tramadol HCl (TRAM) is given concurrently with anticancer drugs for relieving pain. Recently, the world pays attention to green chemistry concept in a trial to decrease the harmful impact of chemicals on our environment. Hence, attempts were performed to find out simple eco-friendly green methods for the simultaneous determination of anticancer agents and analgesics. In this study, two facile green, sensitive spectrofluorimetric approaches were conducted for the estimation of tramadol HCl (TRAM) with axitinib (AXI) or with doxorubicin HCl (DOX). The intrinsic fluorescence of TRAM and AXI was scanned in ethanol in the first approach. The investigation revealed that TRAM could be determined at 297 nm after excitation at 272 nm, while AXI has emission maxima at 401 nm and excitation maxima at 335 nm. In the second approach, aqueous solution/acetate buffer (pH 4.5) was selected as the most convenient solvent for the simultaneous estimation of TRAM and DOX. Intense native fluorescence was recognized for DOX at 592 nm after excitation at 495 nm in addition to determination of TRAM at the previously mentioned wavelength in the first approach. The study outcomes verified that the inherent nature of the solvent has a significant influence on the sensitivity, reproducibility, and quantitation of the method. A good linear correlation was attained between the relative fluorescence and the concentration in the ranges of 0.02–0.4 μg/mL for both TRAM and AXI (the first approach), 0.02–0.24 μg/mL for TRAM and 0.1–1.2 μg/mL for DOX (the second approach). Different dosage forms of the studied drugs were simply analyzed, and good recoveries were attained within the range. Moreover, the proposed approaches were successfully extended for concurrent estimation of the studied drugs in spiked human plasma after simple protein precipitation. According to ICH guidelines, the approaches were assessed regarding linearity, accuracy, and precision. The proposed approaches greenness was confirmed via applying the National Environmental Methods Index, analytical eco-scale and Green Analytical Procedure Index.

A new, robust, and reliable sweeping-micellar electrokinetic chromatography (sweeping-MEKC) method with dynamic pH junction and retention factor gradient effect (RFGE) is developed for the simultaneous determination of four different analytes in two ternary mixtures of pharmaceutical importance. The studied analytes are drotaverine hydrochloride and caffeine combined with paracetamol (Mixture-I) or dipyrone (Mixture-II). Different experimental parameters are carefully investigated in order to achieve the highest possible resolution and sensitivity in a short analysis time. A special interest is given to the effect of sample matrix composition on the attainable enrichment efficiency with a focus on dynamic pH junction and RFGE. Up to 8 times increase in sensitivity is achieved by the modification of the sample matrix. The theoretical considerations of the underlying effects regarding the separation and the enrichment processes are thoroughly discussed. A full validation study of the developed method based on the pharmacopeial guidelines is performed. The method is successfully applied to the analysis of the studied drugs in their co-formulated or single-ingredient tablet preparations with a total run time of less than 11 min.