Development and validation of a quantification method for direct oral anticoagulants from capillary blood using volumetric absorptive microsampling and online SPE-LC-MS

J Chromatogr B Analyt Technol Biomed Life Sci. 2024 Dec 12:1251:124423. doi: 10.1016/j.jchromb.2024.124423. Online ahead of print.

Abstract

The number of prescriptions for new direct oral anticoagulants (DOACs) apixaban, edoxaban, rivaroxaban and dabigatran has increased exponentially in recent years, increasingly replacing the old gold standard, vitamin-K-antagonists. Due to their wide therapeutic range, therapeutic drug monitoring (TDM) is not required, although it has been proven that this could significantly reduce side effects. In order to develop a cost-efficient and simple method for the simultaneous detection of the DOACs and phenprocoumon, a new technology for sample preparation from capillary blood in the ambulant sector named VAMS® was integrated and an LC-MS detector with on-line solid phase extraction (SPE) applying a Turboflow HTLC CycloneTM 1.0x50 mm column was used. The mobile phase consisted of methanol with water (3/97 v/v) and 0.1 % ammonia solution with a flow rate of 2.5 mL/min. For the chromatographic separation, a Phenomenex LTD Kinetex 2.6 µm C18 100 Å, 100x3.0 mm column with a flow rate of 0.3 mL/min in gradient mode was utilized. The mobile phase consisted of acetonitrile, water and formic acid (A: 10:90:0.1 v/v and B: 95:05:0.1 v/v). The method was fully validated in the therapeutic range of the substances according to current guidelines. The LLOQ ranged from 3.5 µg/L for rivaroxaban to 88 µg/L for phenprocoumon and the intra-day and inter-day precision was less than 13 % and 12 %, while the accuracy was within a range of 85.7-113 % and 88.7-106 %, respectively. Samples could be stored in the Mitra® devices for at least seven days at room temperature except of dabigatran. Because the Mitras® were used, exactly 10 µL of blood could be drawn and no significant haematocrit effect was observed. A reliable, simple and cost-effective extraction and analysis LC-MS method could be developed and validated. This method is therefore applicable in ambulatory care.