Andersson Tommy, Weidolf Lars
Clinical Pharmacology and DMPK, AstraZeneca R&D Mölndal, Mölndal, Sweden.
Clin Drug Investig. 2008;28(5):263-79. doi: 10.2165/00044011-200828050-00001.
It is estimated that about half of all therapeutic agents are chiral, but most of these drugs are administered in the form of the racemic mixture, i.e. a 50/50 mixture of its enantiomers. However, chirality is one of the main features of biology, and many of the processes essential for life are stereoselective, implying that two enantiomers may work differently from each other in a physiological environment. Thus, receptors or metabolizing enzymes would recognize one of the ligand enantiomers in favour of the other. With one exception, all presently marketed proton pump inhibitors (PPIs)--omeprazole, lansoprazole, pantoprazole and rabeprazole--used for the treatment of gastric acid-related diseases are racemic mixtures. The exception is esomeprazole, the S-enantiomer of omeprazole, which is the only PPI developed as a single enantiomer drug. The development of esomeprazole (an alkaline salt thereof, e.g. magnesium or sodium) was based on unique metabolic properties that clearly differentiated esomeprazole from omeprazole, the racemate. At comparable doses, these properties led to several clinical advantages, for example higher bioavailability in the majority of patients, i.e. the extensive metabolizers (EMs; 97% in Caucasian and 80-85% in Asian populations), lower exposure in poor metabolizers (PMs; 3% in Caucasian and 15-20% in Asian populations) and lower interindividual variation. For the other, i.e. racemic, PPIs there are some data available on the characteristics of the individual enantiomers, and we have therefore undertaken to analyse the current literature with the purpose of evaluating the potential benefits of developing single enantiomer drugs from lansoprazole, pantoprazole and rabeprazole. For lansoprazole, the plasma concentrations of the S-enantiomer are lower than those of the R-enantiomer in both EMs and PMs, and, consequently, the variability in the population or between EMs and PMs is not likely to decrease with either of the lansoprazole enantiomers. Furthermore, plasma protein binding differs between the two lansoprazole enantiomers, in that the amount of the free S-enantiomer is two-fold higher than that of the R-enantiomer. This will counteract the difference seen in total plasma concentrations of the enantiomers. Also, studies using expressed human cytochrome P450 isoenzymes show that the metabolism of one enantiomer is significantly affected by the presence of the other, which is likely to result in different pharmacokinetics when administering a single enantiomer. For pantoprazole, there is a negligible difference in plasma concentrations between the two enantiomers in EMs, while the difference is substantial in PMs. The difference in AUC between PMs and EMs would decrease to some extent, but in the majority of the population the variability and efficacy would not be altered with a single enantiomer of pantoprazole. The metabolism of the enantiomers of rabeprazole displays stereoselectivity comparable to that of lansoprazole, i.e. the exposure of the R-enantiomer is higher than that of the S-enantiomer in EMs as well as in PMs, which, by analogy to lansoprazole, makes them less suitable for development of a single enantiomer drug. Furthermore, the chiral stability of the rabeprazole enantiomers may be an issue because of significant degradation of rabeprazole to its sulfide analogue, which is subject to non-stereoselective metabolic regeneration of a mixture of the two enantiomers. In conclusion, in contrast to esomeprazole, the S-enantiomer of omeprazole, minimal if any clinical advantages would be expected in developing any of the enantiomers of lansoprazole, pantoprazole, or rabeprazole as compared with their racemates.
据估计,所有治疗药物中约有一半是手性的,但这些药物大多以外消旋混合物的形式给药,即其对映体的50/50混合物。然而,手性是生物学的主要特征之一,许多生命必需过程具有立体选择性,这意味着两种对映体在生理环境中的作用可能不同。因此,受体或代谢酶会优先识别其中一种配体对映体。目前市场上用于治疗胃酸相关疾病的质子泵抑制剂(PPI)——奥美拉唑、兰索拉唑、泮托拉唑和雷贝拉唑——除一种例外,均为外消旋混合物。例外的是埃索美拉唑,它是奥美拉唑的S-对映体,是唯一作为单一异构体药物开发的PPI。埃索美拉唑(及其碱性盐,如镁盐或钠盐)的开发基于独特的代谢特性,这些特性使埃索美拉唑与外消旋体奥美拉唑明显区分开来。在可比剂量下,这些特性带来了一些临床优势,例如大多数患者(即广泛代谢者,白种人中占97%,亚洲人群中占80 - 85%)的生物利用度更高,代谢不良者(白种人中占3%,亚洲人群中占15 - 20%)的暴露量更低,个体间差异更小。对于其他(即外消旋)PPI,已有关于各个对映体特性的一些数据,因此我们着手分析当前文献,目的是评估从兰索拉唑、泮托拉唑和雷贝拉唑开发单一异构体药物的潜在益处。对于兰索拉唑,无论是广泛代谢者还是代谢不良者,S-对映体的血浆浓度均低于R-对映体,因此,无论是在总体人群中还是在广泛代谢者与代谢不良者之间,兰索拉唑任一异构体的变异性都不太可能降低。此外,兰索拉唑的两种对映体与血浆蛋白的结合情况不同,游离S-对映体的量比R-对映体高两倍。这将抵消对映体总血浆浓度的差异。而且,使用表达的人细胞色素P450同工酶进行的研究表明,一种对映体的代谢会受到另一种对映体存在的显著影响,这可能导致给予单一异构体时药代动力学不同。对于泮托拉唑,在广泛代谢者中两种对映体的血浆浓度差异可忽略不计,而在代谢不良者中差异较大。代谢不良者与广泛代谢者之间的AUC差异会在一定程度上减小,但在大多数人群中,泮托拉唑单一异构体的变异性和疗效不会改变。雷贝拉唑对映体的代谢显示出与兰索拉唑相当的立体选择性,即在广泛代谢者和代谢不良者中,R-对映体的暴露量均高于S-对映体,这与兰索拉唑类似,使其不太适合开发单一异构体药物。此外,雷贝拉唑对映体的手性稳定性可能是一个问题,因为雷贝拉唑会大量降解为其硫化物类似物,该类似物会经历两种对映体混合物的非立体选择性代谢再生。总之,与奥美拉唑的S-对映体埃索美拉唑不同,与兰索拉唑、泮托拉唑或雷贝拉唑的外消旋体相比,开发它们的任何一种对映体预计都不会有明显的临床优势。