Determination of enantiomeric composition of fluoxetine by synchronous fluorescence spectrometry coupled with multivariate calibration in biological samples

Abstract

This paper presents rapid and low cost analytical method for the determination of the fluoxetine enantiomeric composition in biological samples (urine). The combination of synchronous fluorescence spectrometry and inverse multivariate calibration methods was used. The chiral recognition of the fluoxetine was based on the creating of the diastereomeric complexes with -cyclodextrin. A net analytical signal of diastereomeric complexes was obtained by the addition of aliquot part of urine into calibration and validation sets. This step ensures the elimination of the urine matrix effect. The synchronous fluorescence spectra at the constant wavelength differences (∆λ) of 30 and 50 nm, based on RMS %RE values, were chosen for chemometric analysis. Principal component regression (PCR) and partial least square method (PLS) were compared to determine the enantiomeric composition. The most suitable results were provided by the PLS model constructed from the synchronous data at ∆λ = 50 nm. The calculated figure of merit was used for validation of proposed method.

Enantiomeric assay of escitalopramS(+)‐enantiomer and its “in‐process impurities” using two different techniques

“…38,39 Recently, synchronous fluorescence spectrometry coupled with multivariate calibration has been reported for enantioseparation of fluoxetine. 40,41 β-Cyclodextrins (β-CD) are the widely used chiral selectors having cyclic oligosaccharides molecule with a hydrophilic outer surface and a hydrophobic inner cavity. The CD cavity provides noncovalent interactions with the chiral analyte.…”

Indirect synchronous fluorescence spectroscopy and direct high‐performance thin‐layer chromatographic methods for enantioseperation of zopiclone and determination of chiral‐switching eszopiclone: Evaluation of thermodynamic quantities of chromatographic separation

“…Calibration graphs 40 of the proposed methods were constructed by plotting the amplitude values of SFS intensities at 296 nm versus eszopiclone concentrations in μg/mL and area under peak (AUP) at 304 nm against eszopiclone concentrations in microgram per band for SFS and HPTLC methods, respectively. The regression analysis data for the described methods were listed ( Table 3).…”

“…a 95% confidence limit. Table 3, based on the standard deviation of intercept (σ) and the slope (s) of the regression line using the following formulas 40 :…”

“…28,29 Since, enantiomers often exhibit different pharmacological and toxicological properties 30 ; therefore, the aim of our work is to develop simple, smart, novel, and inexpensive enantioselective SFS and HPTLC methods for the enantioseparation of zopiclone followed by the evaluation of enantiomeric ratio % of R & S forms and determination of the chiral-switching eszopiclone in drug substances and products using L-(+)-tartaric acid as a chiral selector. 40 HPTLC, the second method, is a direct chiral separation and stereoselective densitometric method for enantioseperation of racemic zopiclone. Earlier, L-(+)tartaric acid and its derivatives have been used by Bhushan et al [31][32][33][34] as a chiral selector impregnated on silica gel TLC plates but also as a chiral mobile-phase additive for the enantiomeric separation.…”

“…37,38 To the best of our knowledge, SFS technique was not reported in the literature for enantioseperation except determination of S-(+)-ofloxacin enantiomer 39 and determination of enantiomeric composition of fluoxetine combined with multivariate calibration method. 40 HPTLC, the second method, is a direct chiral separation and stereoselective densitometric method for enantioseperation of racemic zopiclone. The proposed HPTLC method is advantageous than reported TLC 13 is that we used HPTLC plates not normal TLC plates, which provided faster development time and more resolving power per unit distance.…”