From the Department of Biological Chemistry, Weizmann Institute of Science, Rehovoth 76100, Israel.
the Department of Ophthalmology, Asaf Harofeh Hospital, Zerifin 608183, Israel, and.
J Biol Chem. 2014 Jul 25;289(30):21153-62. doi: 10.1074/jbc.M114.557629. Epub 2014 Jun 10.
In the ciliary epithelium of the eye, the pigmented cells express the α1β1 isoform of Na,K-ATPase, whereas the non-pigmented cells express mainly the α2β3 isoform of Na,K-ATPase. In principle, a Na,K-ATPase inhibitor with selectivity for α2 could effectively reduce intraocular pressure with only minimal local and systemic toxicity. Such an inhibitor could be applied topically provided it was sufficiently permeable via the cornea. Previous experiments with recombinant human α1β1, α2β1, and α3β1 isoforms showed that the classical cardiac glycoside, digoxin, is partially α2-selective and also that the trisdigitoxose moiety is responsible for isoform selectivity. This led to a prediction that modification of the third digitoxose might increase α2 selectivity. A series of perhydro-1,4-oxazepine derivatives of digoxin have been synthesized by periodate oxidation and reductive amination using a variety of R-NH2 substituents. Several derivatives show enhanced selectivity for α2 over α1, close to 8-fold in the best case. Effects of topically applied cardiac glycosides on intraocular pressure in rabbits have been assessed by their ability to either prevent or reverse acute intraocular pressure increases induced by 4-aminopyridine or a selective agonist of the A3 adenosine receptor. Two relatively α2-selective digoxin derivatives efficiently normalize the ocular hypertension, by comparison with digoxin, digoxigenin, or ouabain. This observation is consistent with a major role of α2 in aqueous humor production and suggests that, potentially, α2-selective digoxin derivatives could be of interest as novel drugs for control of intraocular pressure.
在眼睛的睫状上皮细胞中,色素细胞表达 α1β1 同工型的 Na,K-ATP 酶,而非色素细胞主要表达 α2β3 同工型的 Na,K-ATP 酶。原则上,具有针对 α2 的选择性的 Na,K-ATP 酶抑制剂可以有效地降低眼内压,而局部和全身毒性最小。这种抑制剂可以局部应用,只要它通过角膜足够渗透即可。以前使用重组人 α1β1、α2β1 和 α3β1 同工型的实验表明,经典的心脏糖苷地高辛部分是 α2 选择性的,并且三糖苷部分负责同工型选择性。这导致了一个预测,即第三 digitoxose 的修饰可能会增加 α2 选择性。已经通过用过碘酸钠氧化和使用各种 R-NH2 取代基的还原胺化合成了一系列地高辛的全氢-1,4-恶唑嗪衍生物。几种衍生物显示出对 α2 的选择性增强,在最佳情况下接近 8 倍。通过它们预防或逆转 4-氨基吡啶或 A3 腺苷受体选择性激动剂诱导的急性眼内压升高的能力来评估局部应用的心脏糖苷对眼内压的影响。与地高辛、地高辛配基或哇巴因相比,两种相对 α2 选择性的地高辛衍生物能够有效地使眼高压正常化。这一观察结果与α2 在房水产生中的主要作用一致,并表明潜在地,α2 选择性地高辛衍生物可能作为新型药物控制眼内压具有重要意义。