Europium(III)-driven red photoluminescent sensor for ultra-sensitive and reliable assay of sildenafil citrate in pure form, pharmaceutical formulations and Bio-fluids.
Ali Hazim M HM, Essawy Abd El-Naby I AEI, Elnasr Tarek Ahmed Seaf TAS, Essawy Amr A AA
Lanthanide complexes, particularly Eu3+ β-diketonates, offer narrow-band, long-lived red emission ideally suited to sensitive fluorescence assays in complex media. The Eu(TTA)3(H2O)2 chelate combines efficient near-UV excitation, robust emission and labile coordination sites, making its signal highly responsive to molecular binding events. Sildenafil citrate is a widely used PDE-5 inhibitor whose misuse, counterfeiting and potential drug interactions demand reliable monitoring in pharmaceuticals and biological fluids. However, current chromatographic techniques are costly and labor-intensive, creating a pressing need for a simple, robust, low-cost, green, field-deployable optical method for sildenafil quantification. Near-UV excitation around 350 nm efficiently promotes ligand-to-metal energy transfer to the Eu3+ 5D0 level, producing line-narrowed 5D0→7F2 emission at ∼ 614 nm whose intensity is selectively quenched by sildenafil without disturbing its spectral fingerprint. The interaction between the Eu-TTA chemosensor and sildenafil involves a mixed mechanism of dynamic fluorescence deactivation and static "antenna" shelving, governed by photo-induced electron transfer and triplet-triplet energy transfer. Under optimized experimental conditions, the sensing protocol exhibits excellent linear Stern-Volmer behavior for sildenafil concentrations from 0.2 to 8.0 µg mL-1 (r ≈ 0.999), with a limit of detection of 0.036 µg mL-1 and a limit of quantification of 0.121 µg mL-1. Fluorimetric method coupled with SupelcleanTM LC-Florisil SPE cartridge with 2-propanol elution solvent was used for the selective determination of sildenafil in human serum and urine avoiding the presence of interference. Analysis of sildenafil in pharmaceutical formulations, spiked human urine and serum affords high overall accuracy and precision, with recoveries of 95.26-99.12 %, 97.5-102.4 % and 93.7-102.3 % and RSD values of 1.29-1.35 %, 1.16-2.01 and 1.21-2.71, respectively, while AGREE and BAGI metrics confirm the method's strong greenness and practical applicability. Consequently, the Eu-TTA-based fluorimetric probe provides a simple, sensitive, and low-cost analytical platform for sildenafil determination in pharmaceutical formulations and biological matrices, with satisfactory accuracy, precision, and practical applicability. Moreover, the system probing performance surpasses existing spectrophotometric methods and rivals chromatographic techniques in sensitivity while offering significant operational simplicity, high throughput, and cost efficiency, thus providing a green and clinically relevant alternative platform.