Department of Medicinal Chemistry, University of Florida, Gainesville, FL 32610-0485, United States.
Center for Pharmacogenomics, College of Pharmacy, University of Florida, Gainesville, FL 32610-0486, United States.
Chem Biol Interact. 2014 May 25;215:33-9. doi: 10.1016/j.cbi.2014.02.015. Epub 2014 Mar 13.
The in vivo elimination rate of dichloroacetate (DCA), an investigational drug; is determined by the rate of its biotransformation to glyoxylate, catalyzed by glutathione transferase ζ1 (GSTZ1). DCA is a mechanism-based inactivator of GSTZ1, thus elimination of DCA is slowed with repeated dosing. We observed that chloride, a physiologically important anion, attenuated DCA-induced GSTZ1 inactivation in human liver cytosol in a concentration and GSTZ1 haplotype-dependent way. In the absence of chloride, incubation with 0.5mM DCA resulted in inactivation of GSTZ1 with a half-life of 0.4h (samples with the KRT haplotype) to 0.5h (EGT haplotype). At the hepatic physiological chloride concentration, 38mM, samples with the EGT haplotype retained more activity (80%) following a 2-h incubation with 0.5mM DCA than those possessing the KRT haplotype (55%). The chloride concentration that protected 50% of the GSTZ1 activity following 2-h incubation with 0.5mM DCA (EC50) was 15.0±3.1mM (mean±S.D., n=3) for EGT samples and 36.2±2.2mM for KRT samples. Bromide, iodide and sulfite also protected GSTZ1 from inactivation by DCA, however fluoride, sulfate, carbonate, acetate, cyanide did not. Protection by bromide varied by GSTZ1 haplotype: EC50 was 1.3±0.3mM for the EGT haplotype and 5.0±0.60mM for the KRT haplotype. The EC50 values for iodide and sulfite in liver cytosol samples with EGT haplotype were respectively 0.14±0.06mM and 9.6±1.1mM (mean±S.D., n=3). Because the in vivo half-life of DCA is determined by the fraction of active GSTZ1 in the liver, identifying factors that regulate GSTZ1 activity is important in determining appropriate DCA dosing in humans.
二氯乙酸(DCA)是一种研究药物,其体内消除率由其被谷胱甘肽转移酶 ζ1(GSTZ1)催化生物转化为乙醛酸的速率决定。DCA 是 GSTZ1 的一种基于机制的失活剂,因此随着重复给药,DCA 的消除速度会减慢。我们观察到,氯离子作为一种生理上重要的阴离子,以浓度和 GSTZ1 单倍型依赖的方式,减弱了人肝胞质中二氯乙酸诱导的 GSTZ1 失活。在没有氯离子的情况下,与 0.5mM DCA 孵育导致 GSTZ1 失活,半衰期为 0.4h(具有 KRT 单倍型的样品)至 0.5h(具有 EGT 单倍型的样品)。在肝的生理氯离子浓度 38mM 下,与 0.5mM DCA 孵育 2 小时后,具有 EGT 单倍型的样品比具有 KRT 单倍型的样品保留更多的活性(80%)(70%)。在与 0.5mM DCA 孵育 2 小时后,保护 50%GSTZ1 活性所需的氯离子浓度(EC50)分别为 15.0±3.1mM(平均值±S.D.,n=3)(EGT 样品)和 36.2±2.2mM(KRT 样品)。溴化物、碘化物和亚硫酸盐也能保护 GSTZ1 免受 DCA 的失活,但氟化物、硫酸盐、碳酸盐、乙酸盐、氰化物则不能。溴化物对 GSTZ1 的保护作用因 GSTZ1 单倍型而异:对于 EGT 单倍型,EC50 为 1.3±0.3mM;对于 KRT 单倍型,EC50 为 5.0±0.60mM。在具有 EGT 单倍型的肝胞质样品中,碘化物和亚硫酸盐的 EC50 值分别为 0.14±0.06mM 和 9.6±1.1mM(平均值±S.D.,n=3)。由于 DCA 的体内半衰期由肝中活性 GSTZ1 的分数决定,因此确定调节 GSTZ1 活性的因素对于确定人类中 DCA 的适当剂量非常重要。