Ralaniten is a substrate for O-glucuronidation
by UGT2B enzymes.
(A) Chemical structures of ralaniten, EPI-045, and major glucuronide
of ralaniten M15 (EPI-002053). Potential sites of glucuronidation
are shown in red. (B) HPLC chromatograms show glucuronidated products
following incubation in the presence of UDPGA cofactor. While some
minor peaks are observed in samples incubated with EPI-045 (labeled
045-G), the intensity is substantially lower than that seen in those
incubated with ralaniten. Cotreatment with β-glucuronidase is
sufficient to remove glucuronides from substrate, and thus only peaks
indicating unbound drugs are seen. (C) Detection of ralaniten metabolites
using LC/MS following incubation with human hepatocytes. Direct glucuronidation
of ralaniten represents the most prevalent metabolite (M15). Another
notable metabolite, M4, represents dechlorination followed by cysteine
conjugation. (D) LC–MS chromatographs showing ralaniten metabolites
isolated from pooled human plasma samples (ESSA Pharma, Inc.). Patients
were treated with 3600 mg of ralaniten acetate daily. M15 represents
direct glucuronidation, M19 is an oxidized metabolite. (E) Dose response
curves measuring androgen-dependent growth of LNCaP cells treated
with escalating concentrations of ralaniten or EPI-002053 (synthetic
ralaniten glucuronide structurally equivalent to M15) and stimulated
with 0.1 nM R1881. IC50 values were calculated using a
linear regression and interpolation/extrapolation where the line crossed
50% growth. RAL, 14.78 μM; EPI-002053, >35 μM; p = 0.007. Data presented as mean ± SEM and analyzed
by two-way ANOVA with Sidak’s test applied post hoc, n = 4 independent experiments. (F) Transcript
levels of AR, PSA, FKBP5, and RHOU normalized to SDHA harvested
from LNCaP cells treated with RAL (35 μM), EPI-002053 (35 μM)
or v/v DMSO vehicle and stimulated with 1 nM R1881. Data presented
as mean ± SEM and analyzed by one-way ANOVA with Dunnett’s
test applied post hoc, n = 4 independent
experiments. (G) Protein levels of AR and AR regulated genes from
whole cell lysates (LNCaP) treated as in part F. *p < 0.05; **p < 0.01; ***p < 0.001; #p < 0.0001; n.s., not
significant. RAL, ralaniten.