Department of Pathology and Immunology, Washington University School of Medicine, Campus Box 8118, 660 S. Euclid Ave., St. Louis, Missouri 63110, United States.
J Chem Inf Model. 2023 Mar 27;63(6):1675-1694. doi: 10.1021/acs.jcim.2c01383. Epub 2023 Mar 16.
Cytochrome P450 enzymes aid in the elimination of a preponderance of small molecule drugs, but can generate reactive metabolites that may adversely react with protein and DNA and prompt drug candidate attrition or market withdrawal. Previously developed models help understand how these enzymes modify molecule structure by predicting sites of metabolism or characterizing formation of metabolite-biomolecule adducts. However, the majority of reactive metabolites are formed by multiple metabolic steps, and understanding the progenitor molecule's network-level behavior necessitates an integrative approach that blends multiple site of metabolism and structure inference models. Our previously developed tool, XenoNet 1.0, generates metabolic networks, where nodes are molecules and weighted edges are metabolic transformations. We extend XenoNet with a bidirectional message passing neural network that integrates edge feature information and local network structure using edge-conditioned graph convolutions and jumping knowledge to predict the authenticity of inferred Phase I metabolite structures. Our model significantly outperformed prior work and algorithmic baselines on a data set of 311 networks and 6606 intermediates annotated using a chemically diverse set of 20 736 individual in vitro and in vivo reaction records accounting for 92.3% of all human Phase I metabolism in the Accelrys Metabolite Database. Cross-validated predictions resulted in area under the receiver operating characteristic curves of 88.5% and 87.6% for separating experimentally observed and unobserved metabolites at global and network levels, respectively. Further analysis verified robustness to networks of varying depth and breadth, accurate detection of metabolites, such as d,l-methamphetamine, that are experimentally observed or unobserved in different network contexts, extraction of important metabolic subnetworks, and identification of known bioactivation pathways, such as for nimesulide and terbinafine. By exploiting network structures, our approach accurately suggests unreported metabolites for experimental study and may rationalize modifications for avoiding deleterious pathways antecedent to reactive metabolite formation.
细胞色素 P450 酶有助于消除大量小分子药物,但会产生可能与蛋白质和 DNA 发生不良反应的反应性代谢物,并促使药物候选物淘汰或退出市场。以前开发的模型有助于通过预测代谢部位或表征代谢物-生物分子加合物的形成来理解这些酶如何修饰分子结构。然而,大多数反应性代谢物是由多个代谢步骤形成的,要了解前体分子的网络级行为,需要采用融合多种代谢部位和结构推断模型的综合方法。我们之前开发的工具 XenoNet 1.0 生成代谢网络,其中节点是分子,加权边是代谢转化。我们使用带条件边的图卷积和跳跃知识扩展了 XenoNet,将边特征信息和局部网络结构集成到双向消息传递神经网络中,以预测推断的 I 相代谢物结构的真实性。我们的模型在使用一组化学多样化的 20736 个个体体外和体内反应记录注释的 311 个网络和 6606 个中间体的数据集上的表现明显优于先前的工作和算法基线,该数据集涵盖了 Accelrys 代谢物数据库中 92.3%的所有人类 I 相代谢。交叉验证预测在全局和网络级别分别得到 88.5%和 87.6%的接收器操作特征曲线下面积,用于分离实验观察到和未观察到的代谢物。进一步的分析验证了该方法对不同深度和广度的网络的稳健性、对 d,l-苯丙胺等实验观察到或在不同网络环境中未观察到的代谢物的准确检测、重要代谢子网络的提取以及尼美舒利和特比萘芬等已知生物激活途径的识别。通过利用网络结构,我们的方法可以准确地为实验研究建议未报道的代谢物,并可以在形成反应性代谢物之前合理化避免有害途径的修饰。