Nails can stably accumulate substances for long periods of time, thus providing retrospective information regarding drugs of abuse and pharmaceutical use. Nails have several advantages over the conventional matrices, such as blood and urine, including a longer detection window (months to years), non-invasive sample collection, and easy storage and transport. These aspects make nails a very interesting matrix for forensic and clinical toxicology. Because of the low concentrations of drugs of abuse and pharmaceuticals present in nails and the complexity of the keratinized matrix, analytical methods need to be more sensitive, and sample preparation is crucial. This review summarizes the literature regarding the detection and quantification of drugs of abuse and pharmaceuticals in nails, as well as the employed pre-analytical and analytical techniques. Additionally, the applications of nail analysis are reviewed. Finally, an overview of the challenges of nail analysis is provided, and guidelines for future research are proposed.
To quantify alcohol use, objective, specific and sensitive long-term alcohol markers are necessary. Ethyl glucuronide (EtG), a direct metabolite of alcohol, accumulates in keratinous matrices such as hair and nails, and is a specific and sensitive long-term biomarker for the detection of chronic alcohol consumption. So far, research has primarily focused on the detection of EtG in hair, and studies on its measurement in nails are scarce. In this article, we assessed EtG concentrations in hair, finger- and toenails from the same individuals in order to evaluate the direct correlation between the matrices. To this end, a total amount of 45 hair, 41 fingernail, and 13 toenail samples were collected from patients treated for alcohol use disorders at two psychiatric centers in Belgium. Samples were analyzed by gas chromatography-tandem mass spectrometry. Hair EtG concentrations ranged from 123pg/mg for chronic excessive alcohol consumption, 59-123pg/mg for moderate alcohol consumption, and <59pg/mg for alcohol abstinence. In light of these results, nails may be a useful alternative to hair samples for monitoring of long-term alcohol consumption, e.g., in cases where hair is not available. Further studies are needed to establish cut-off values for EtG levels in nails.
Ethyl glucuronide (EtG), a minor metabolite of ethanol, accumulates in hair and is currently used as a long-term marker for the detection of chronic and excessive alcohol consumption. Sensitive methods are required to differentiate teetotalers from moderate drinkers according to the established cut-off (i.e., 7 pg/mg hair). The aim of this study was to develop a sensitive method using gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) operated in the negative ion chemical ionization (NICI) mode. The validated method was applied to hair samples from teetotalers, moderate and excessive alcohol consumers, and results were compared to a previously validated GC-NICI-MS method. The developed GC-NICI-MS/MS method showed linearity over a range from 2 to 400 pg/mg hair, with a limit of detection (LOD) of 0.05 pg/mg hair and a lower limit of quantification (LLOQ) of 0.2 pg/mg hair, compared to an LOD of 0.5 pg/mg hair and LLOQ of 1.5 pg/mg hair obtained with GC-NICI-MS. Furthermore, lower background noise was observed using GC-NICI-MS/MS. Comparison of results of hair samples (n=58) obtained by GC-NICI-MS and GC-NICI-MS/MS showed no significant difference between both methods (paired-sample t-test, p>0.05; mean CV=1.0%). The differences between both methods were larger for EtG concentrations<30 mg/pg hair (mean CV=1.7%) than for EtG concentrations>30 mg/pg hair (mean CV=0.7%). This suggests a higher selectivity of GC-NICI-MS/MS at lower concentrations. In conclusion, by using GC-NICI-MS/MS, a higher analytical selectivity and an improved signal to noise ratio, can be achieved. Although GC-NICI-MS would not change the interpretation of the EtG concentrations, the present GC-NICI-MS/MS method should preferentially be used for the determination of EtG in hair, especially when differentiating between teetotalers and moderate drinkers according to the current cut-off (i.e., 7 pg/mg hair).
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