RESUMO
An optical sensor (OS) was synthesized by mixing 10,12-pentacosadiinoic acid (PDA) with a triblock copolymer for use in the detection/quantification of lidocaine (LD) in seized cocaine hydrochloride (seized CH) samples. In the presence of LD, the OS presented a chromatic transition from blue to red, while no chromatic transition was observed for other typical cocaine adulterants or cocaine hydrochloride. Isothermal titration calorimetry analysis revealed specific interactions between the PDA molecules of the OS and the LD molecules, with these interactions being enthalpically favorable (-1.20 to -36.7 kJ mol-1). Therefore, the OS color change only occurred when LD was present in the sample, making the OS selective for LD. Consequently, LD was successfully detected in seized CH samples, irrespective of the type of adulteration. The OS was used for the quantification of LD in seized CH samples containing different adulterants, providing a linear range of 0.0959 to 0.225% (w/w), a precision of 7.2%, an accuracy ranging from -10 to 10%, and limits of detection and quantification of 0.0110% (w/w) and 0.0334% (w/w), respectively.
Assuntos
Cocaína , Contaminação de Medicamentos , LidocaínaRESUMO
Life manifestation is mainly based on biopolymer-ligand molecular recognition; therefore, the elucidation of energy and speed associated with protein-ligand binding is strategic in understanding and modulating biological systems. In this study, the interactions between methylene blue (MB) or azure A (AZA) dyes and bovine lactoferrin (BLF) were investigated by surface plasmon resonance, fluorescence spectroscopy, and isothermal titration microcalorimetry. Despite the molecular similarities between the dyes, the BLF-AZA binding thermodynamic parameters (ΔGAZAo = -30.50 and ΔHAZAo = 10.8 (kJ·mol-1)) were higher in magnitude than those of the BLF-MB systems (ΔGMBo = -27.3 and ΔHMBo = 5.72 (kJ·mol-1)). To increase the systems' entropy (TΔSAZAo = 41.3 and TΔSMBo = 33.0 (kJ·mol-1)), the hydrophobic interactions must outweigh the electrostatic repulsion, thereby promoting BLF-dye binding. The activation complex formation (Eac, aMB = 33, Eac, aAZA = 32, ∆Ha, MB = 31, ∆Ha, AZA = 30, ∆Ga, MB = 51.84, ∆Ga, AZA = 50.7, T∆Sa, MB = -21, T∆Sa, AZA = -21 (kJ·mol-1)), owing to free BLF and MB (or AZA) associations, was not affected by the dye chemical structure, while for the thermodynamically stable BLF-dye complex dissociation, the same energetic parameters (Eac, dMB = 16, Eac, dAZA = 6.4, ∆Hd, MB = 14, ∆Hd, AZA = 3.9, ∆Gd, MB = 81.4, ∆Gd, AZA = 74.93, T∆Sd, MB = -68, T∆Sd, AZA = -71.0 (kJ·mol-1)) were considerably affected by the number of methyl groups. Our results may be very useful to determine binding processes controlled by kinetic parameters, as well as to optimize the application of these photosensitive dyes in biological systems.