1H NMR determination of adulteration of anabolic steroids in seized drugs

Abstract

Counterfeiting and adulteration of pharmaceuticals is a prevalent problem worldwide and represents a major health risk to the population, with anabolic steroids being one of the main classes of drugs consumed and obtained from dubious sources. In this work, we propose the use of the H NMR technique to evaluate formulations containing anabolic steroids, with analysis of 40 samples of anabolic drugs that are used in injectable and capsule forms. The samples analyzed presented the following active ingredients: testosterone propionate, testosterone phenylpropionate, testosterone isocaproate, testosterone decanoate, testosterone cypionate, testosterone undecanoate, stanozolol, drostanolone propionate, trenbolone acetate, oxymetholone, and methandrostenolone. TheH NMR spectroscopic measurements were performed using a 600 MHz Bruker Avance III spectrometer, with deuterated chloroform (CDCl) containing 0.1% TMS as solvent. Of the 40 samples analyzed, eight did not show the presence of the active principle stated on the label. Three types of adulteration were found in the analyzed samples: absence of the active ingredient, adulteration with other substances, and concentration values below those indicated on the label. Sildenafil citrate was found in four samples. The GC-MS technique was used to confirm the adulteration results found using H NMR. Quantitative determination by NMR was performed using internal standard and ERETIC 2 methods, and the results obtained were statistically the same.

Anabolic androgenic steroid abuse in the United Kingdom: An update

“…These are not pharmaceutical and the content of anabolic androgenic steroids purchased online cannot be guaranteed. Products have widely been identified as counterfeit, misleadingly named, and labelled with incorrect contents and dosages (Abbate et al, ; Coomber, Pavlidis, Wilde, Schmidt, & Redshaw, ; Cordaro et al, ; da Justa Neves, Marcheti, & Caldas, ; de Moura Ribeiro, Boralle, Felippe, Pezza, & Pezza, ; Graham et al, ; Weber, Kamber, Lentillon‐Kaestner, Krug, & Thevis, ). Thus, despite carefully planned administration regimes, users cannot be sure that what they purchase really contains the substance they need, at the correct dose.…”

Analysis of seized stanozolol formulations in South Brazil by liquid chromatography coupled to quadrupole time-of-flight-mass spectrometry

“…These results exhibit correlation with other studies conducted in Brazil. Berneira (14). Neves et al has shown that 53% of the AAS were counterfeit including stanozolol samples that did not present the active ingredient and exhibited lower or higher amount than the indicated (13).…”

“…The measurements conducted by Ribeiro et al indicated that 20% of seized AAS samples analyzed showed adulterants not described in the labels. Among those, stanozolol samples presented the most unusual results since none of the capsules had the analyte presence, showing adulteration with other AAS compounds and sildenafil citrate (14). Stanozolol (STZ) is an alkylated C17α steroid commonly detected SSFFC medical product in Brazilian scenario (9).…”

“…Also, it can be evaluated in pharmaceutical formulations in order to determine its authenticity. In this scenario, chromatographic approaches are the most established methodologies (14). Gas chromatography coupled to mass spectrometry (MS) is widely used for screening, while liquid chromatography coupled to MS or tandem mass spectrometry (MS/MS) ensures the required analysis precision, specificity and sensibility with minimal sample pretreatment (18,19).…”

“…Gas chromatography coupled to mass spectrometry (MS) is widely used for screening, while liquid chromatography coupled to MS or tandem mass spectrometry (MS/MS) ensures the required analysis precision, specificity and sensibility with minimal sample pretreatment (18,19). Moreover, spectroscopic methods such as proton nuclear magnetic resonance (1H NMR), Raman and Fourier transform infrared spectroscopy (FT-IR) can be applied to the identification and quantitation of stanozolol (14,20). In addition, the use of high-resolution mass spectrometry (HRMS) methods is suggested due to the ability to improve mass accuracy and enhance the selectivity of the target compounds and/or allow for the analysis of untargeted compounds.…”