Cater Michael A, Pearson Helen B, Wolyniec Kamil, Klaver Paul, Bilandzic Maree, Paterson Brett M, Bush Ashley I, Humbert Patrick O, La Fontaine Sharon, Donnelly Paul S, Haupt Ygal
Research Division, Peter MacCallum Cancer Centre, East Melbourne, Victoria 3002, Australia.
ACS Chem Biol. 2013 Jul 19;8(7):1621-31. doi: 10.1021/cb400198p. Epub 2013 May 24.
The therapeutic efficacy of two bis(thiosemicarbazonato) copper complexes, glyoxalbis[N4-methylthiosemicarbazonato]Cu(II) [Cu(II)(gtsm)] and diacetylbis[N4-methylthiosemicarbazonato]Cu(II) [Cu(II)(atsm)], for the treatment of prostate cancer was assessed in cell culture and animal models. Distinctively, copper dissociates intracellularly from Cu(II)(gtsm) but is retained by Cu(II)(atsm). We further demonstrated that intracellular H2gtsm [reduced Cu(II)(gtsm)] continues to redistribute copper into a bioavailable (exchangeable) pool. Both Cu(II)(gtsm) and Cu(II)(atsm) selectively kill transformed (hyperplastic and carcinoma) prostate cell lines but, importantly, do not affect the viability of primary prostate epithelial cells. Increasing extracellular copper concentrations enhanced the therapeutic capacity of both Cu(II)(gtsm) and Cu(II)(atsm), and their ligands (H2gtsm and H2atsm) were toxic only toward cancerous prostate cells when combined with copper. Treatment of the Transgenic Adenocarcinoma of Mouse Prostate (TRAMP) model with Cu(II)(gtsm) (2.5 mg/kg) significantly reduced prostate cancer burden (∼70%) and severity (grade), while treatment with Cu(II)(atsm) (30 mg/kg) was ineffective at the given dose. However, Cu(II)(gtsm) caused mild kidney toxicity in the mice, associated primarily with interstitial nephritis and luminal distention. Mechanistically, we demonstrated that Cu(II)(gtsm) inhibits proteasomal chymotrypsin-like activity, a feature further established as being common to copper-ionophores that increase intracellular bioavailable copper. We have demonstrated that increasing intracellular bioavailable copper can selectively kill cancerous prostate cells in vitro and in vivo and have revealed the potential for bis(thiosemicarbazone) copper complexes to be developed as therapeutics for prostate cancer.
在细胞培养和动物模型中评估了两种双(硫代半卡巴腙)铜配合物,即乙二醛双[N4-甲基硫代半卡巴腙]铜(II)[Cu(II)(gtsm)]和二乙酰双[N4-甲基硫代半卡巴腙]铜(II)[Cu(II)(atsm)]对前列腺癌的治疗效果。独特的是,铜在细胞内从Cu(II)(gtsm)解离,但被Cu(II)(atsm)保留。我们进一步证明,细胞内的H2gtsm [还原的Cu(II)(gtsm)]继续将铜重新分配到生物可利用(可交换)池中。Cu(II)(gtsm)和Cu(II)(atsm)均能选择性地杀死转化的(增生性和癌性)前列腺细胞系,但重要的是,不影响原代前列腺上皮细胞的活力。增加细胞外铜浓度可增强Cu(II)(gtsm)和Cu(II)(atsm)的治疗能力,并且它们的配体(H2gtsm和H2atsm)仅在与铜结合时对癌性前列腺细胞有毒性。用Cu(II)(gtsm)(2.5 mg/kg)治疗小鼠前列腺转基因腺癌(TRAMP)模型可显著降低前列腺癌负担(约70%)和严重程度(分级),而用Cu(II)(atsm)(30 mg/kg)在给定剂量下无效。然而,Cu(II)(gtsm)在小鼠中引起轻度肾毒性,主要与间质性肾炎和管腔扩张有关。从机制上讲,我们证明Cu(II)(gtsm)抑制蛋白酶体类胰凝乳蛋白酶样活性,这一特征进一步被确认为增加细胞内生物可利用铜的铜离子载体所共有。我们已经证明,增加细胞内生物可利用铜可以在体外和体内选择性地杀死癌性前列腺细胞,并揭示了双(硫代半卡巴腙)铜配合物作为前列腺癌治疗药物的开发潜力。