Detection of Counterfeit Durateston® Using Fourier Transform Infrared Spectroscopy and Partial Least Squares - Discriminant Analysis

Abstract

Medicines containing anabolic steroids are one of the main targets for counterfeiting worldwide, including Brazil. The aim of this work was to propose a method for discriminating original and counterfeit Durateston ® ampoules by Fourier transform infrared spectroscopy (FTIR) followed by chemometric analysis. Ninety-six ampoules of Durateston ® , 49 originals and 47 counterfeits, were analyzed by gas chromatography with mass spectrometry (GC-MS) and by FTIR. Principal component analysis was applied to the infrared spectra to detected different clusters, corresponding to original samples and different types of counterfeits. A partial least squares -discriminant analysis method was proposed to discriminate original samples from those counterfeits that were indistinguishable from the originals in the infrared analysis. A training subset comprised of onethird of the available spectra was used to establish a suitable model that correctly discriminated all samples in the test subset, resulting in 0% of false positive or negative results and 100% of efficiency rate, sensitivity and specificity. In addition to the low cost of the infrared technique, the proposed method is fast, reliable and suitable to replace GC-MS methods used in Durateston ® ampoule analyses to detect counterfeiting.

Forensic analysis of anabolic steroids tablets composition using attenuated total reflection Fourier transform infrared microspectroscopy (µATR‐FTIR) mapping

“…Various analytical techniques have already been applied for the forensic analysis of anabolic drugs, including high-performance liquid chromatography with ultraviolet and mass spectrometry detection [27][28][29], gas chromatography coupled to mass [30][31][32] and nitrogen-phosphorus detectors [32], middle [27][28][29][30][31][32][33] or near [5] infrared spectroscopy, Raman spectroscopy [5], direct analysis real-time (DART) mass spectrometry [34]. However, there is an urgent need to explore the microspectroscopy and chemical mapping techniques for the analysis of these products.…”

Analytical approaches applied to the analysis of apprehended formulations of anabolic androgenic steroids

“…However, for the other samples, it was not possible to identify clear distinctions because testosterone and nandrolone esters as they differ only in the carbon length of their side chains. Moreover, the oily formulation and the vehicle interfered in the resulting spectra with additional bands, possibly masking characteristic vibrations of the anabolic agents 23 . Finally, analysis of product 9 revealed the presence of the excipient carboxymethylcellulose, which was not observed in the chromatographic analysis.…”

“…The counterfeit pharmaceutical materials analyzed in the current work also can be a potential threat to public health as these formulations are usually manufactured under conditions that do not follow sterile guidance, increasing their susceptibility for microbiological contamination 3,5,23 . Additionally, the chemical composition of the products is uncertain as there is no overview from regulatory agencies, which could increase the side effects associated with the use of AASs and risk to the health of the user to alarming levels 8 …”

“…Given these results and previous statistical analysis, there was an indication that the oily excipient could be a biomarker for the discrimination of counterfeit from genuine samples. However, further parameters should be included in order to satisfactorily discriminate the samples 23 …”

“…It should be noted that PCA has not been used currently for this purpose in the analysis of AASs, even though previous reports indicated the use of particular bands found in IR spectroscopy analysis as indicative of falsification in preparations of anabolic agents 23 . Therefore, the application of PCA provided noteworthy insights concerning the composition of the oily excipient that could efficiently be used to identify possible signs of counterfeit materials.…”