Acs reagent grade formic acid

Dapivirine (TMC120 (4-[[4-[(2,4,6-trimethylphenyl)-amino]-2-pyrimidinyl]amino]benzonitrile)) was purchased from Toronto Research Chemicals (North York, ON, Canada) in powdered form. The deuterated internal standard ²H₄-dapivirine was obtained from the International Partnership for Microbicides (IPM; Silver Spring, MD, USA) in powdered form (Figure 1). Drug-free human breast milk was purchased from BioIVT (Westbury, NY, USA). Optima-grade acetonitrile, methanol, water, 0.1% formic acid in water and certified ACS plus grade ammonium hydroxide were purchased from Fisher Scientific (Fairlawn, NJ, USA). ACS reagent grade formic acid was purchased from Sigma Aldrich (St. Louis, MO, USA). HPLC grade n-Hexane was purchased from Alfa Aesar (Haverhill, MA, USA).

Certified reference materials of 5α-dihydrotestosterone (DHT, 1.00 mg/mL in methanol), 5α-dihydrotestosterone-16,16,17-d₃ (DHT-d₃, 100 μg/mL in methanol), 5α-androstane-3α,17β-diol (α-diol, 1.00 mg of lyophilized powder), 5α-androstan-3α,17β-diol-16,16,17-d₃ (α-diol-d₃, 1.00 mg of lyophilized powder), 5α-androstan-3β,17β-diol (β-diol, 1.00 mg of lyophilized powder), and 5α-androstan-3β,17β-diol- 16,16,17-d₃ (β-diol-d₃, 1.00 mg of lyophilized powder) were purchased from Cerilliant Corporation (Round Rock, Texas, USA) (Fig. 2). ACS-reagent-grade formic acid, activated charcoal, triethylamine (TEA), tetrahydrofuran (THF), 2-picolinic acid (PA), 4-(dimethylamino) pyridine (DMAP), 2-methyl-6-nitrobenzoic anhydride (MNBA), and 2-fluoro-1-methylpyridine (FMP) were purchased from Sigma-Aldrich (St. Louis, MO, USA). LC/MS-grade methanol, LC/MS-grade acetonitrile, HPLC-grade water, methyl-tertiary-butyl ether (MTBE), ethyl acetate, and hexane were purchased from Fisher Scientific (Pittsburgh, PA, USA). Six pooled blank mouse sera with specified lot numbers (IR12–061102, IR12–061101, IR12–9010, 10698, 10193, 10832) were purchased from Innovative Research (Novi, MI, USA).

D-(−)-norgestrel (levonorgestrel; LNG), etonogestrel (ETO), medroxyprogesterone 17-acetate (MPA), norethisterone (NET), and their deuterated internal standards, D-(−)-norgestrel-d7 (LNG-IS), etonogestrel-d7 (ETO-IS), medroxyprogesterone-d6 17-acetate (MPA-IS), norethisterone-d7 (NET-IS), were acquired from Toronto Research Chemicals (North York, ON, Canada) in powdered form. Structures of LNG, ETO, MPA, and NET are shown in Figure 1. Drug-free K₂EDTA plasma and whole blood were purchased from BioIVT (Westbury, NY, USA). Optima-grade methanol, water, acetonitrile, ammonium hydroxide, and HPLC-grade methyl-tert-butyl ether and dimethyl sulfoxide were purchased from Fisher Scientific (Fairlawn, NJ, USA). ACS reagent grade formic acid was purchased from Sigma Aldrich (St. Louis, MO, USA).

Cabotegravir and its isotopically labelled internal standard, Cabotegravir-¹⁵N, ¹³C, ²H₂ (CAB-IS), were provided by GlaxoSmithKline in powdered form. Rilpivirine and its deuterated internal standard, rilpvirine-²H₆ (RPV-IS), were acquired from Toronto Research Chemicals (North York, ON, Canada) in powdered form. Structures of CAB and RPV are shown in Figure 1. Drug-free K₂EDTA whole blood (35% hematocrit) was purchased from BioIVT (Westbury, NY, USA). Optima-grade acetonitrile, methanol, water, HPLC-grade dimethyl sulfoxide, and certified ACS grade sodium hydroxide were purchased from Fisher Scientific (Fairlawn, NJ, USA). ACS reagent grade formic acid and 10 M ammonium formate were purchased from Sigma Aldrich (St. Louis, MO, USA). ACS reagent grade ethylenediaminetetraacetic acid (EDTA) was purchased from JT Baker (Center Valley, PA).