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Endocrine Disruptors Modeling the Intracellular Response Global Challenges

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ENDOCRINE DISRUPTORS: MODELING THE INTRACELLULAR RESPONSE Michael Breen, Rory Conolly National Center for Computational Toxicology, U.S. EPA, Research Triangle Park, NC, USA R16-14 ABSTRACT Scientists have identified alterations in the concentration dynamics of specific hormones as risk factors for common cancers such as breast cancer (estrogen, progesterone), endometrial cancer (estrogen), and prostate cancer (estrogen, testosterone). These adverse hormonal changes in the tightly regulated endocrine pathways can be induced from exposure to exogenous endocrine disruptors. Chemicals capable of acting as endocrine disruptors are ubiquitous with environmental sources that include household detergents, pesticides, plastics, pharmaceutical estrogens, industrial chemicals, and byproducts of incineration, paper production, and fuel combustion. Ecological exposures to endocrine disruptors are primarily from industrial and waste water treatment effluents, while human exposures are mainly through the food chain. The adverse effects induced by exposure to endocrine disruptors can be mediated through alterations in the enzymes involved in steroid synthesis. We are developing a mechanistic mathematical model of the intratesticular and intraovarian metabolic network that mediates steroid synthesis to describe the dose-response for endocrine disruptors, and to identify and link new robust molecular biomarkers of exposure that are indicative of the ultimate adverse effects. The deterministic model describes the biosynthetic pathways for the conversion of cholesterol to the sex steroid hormones (estradiol, testosterone, and 11-ketotestosterone) secreted by the testes in fish. The model includes the intermediate metabolites and enzymatic reactions for the multiple pathways involved in the biosynthesis of the sex steroids. Changes in the concentration dynamics of the secreted hormones are used as an index of the endocrine disruption. The initial concentrations and enzyme kinetic reaction rates were taken from the literature or set to biologically reasonable values. This mechanistic model allows for an improved understanding of the source-to-outcome linkages and dynamic dose-response behavior at the molecular level for effective use of biomarkers for risk assessments with endocrine disruptors, including their possible effects on endocrine-induced cancers. Since the biosynthetic pathways for the sex steroids are evolutionarily conserved to a significant extent, this model is likely to also be relevant for mammalian species. LINKING BIOMARKERS OF EXPOSURE TO EFFECTS Molecular Biological Effects Receptor-ligand interaction, DNA binding, enzyme activity COMPUTATIONAL MODEL Intratesticular Steroidogenic Pathway v1 CHOL EDC EXPOSURES • • • • • Exposure of male and female fathead minnows to EE2 (synthetic estrogen): high ecological/regulatory relevance Dose levels: 0 (control), 10, 100 mg/L Dosing phase: 8 days Recovery phase: 8 days Tissue sampling: day 1, 4, 8, and 16 Cellular Altered signaling, gene activation, protein synthesis Organ Altered physiology and tissue morphology Individual Impaired development and reproduction, cancer, death Population Structure, Extinction v2 P450c17 (hydroxylase) 3ßHSD v5 PROG PREG P450scc 17­ PREG v3 P450c17 (lyase) v6 DHA v4 17ßHSD v7 DIOL v15 v8 v14 v11 11-T v16 KT 11ßHSD Biomarkers mRNA, protein, enzyme levels Metabolite profiles Functional and structural change (pathology) Altered reproduction or development Decreased number of animals v9 17­ PROG v10 DIONE P45011ß v17 T v18 P450arom v12 v13 v19 19-T E2 v20 ESTRO NE Computational model Small fish model Systems biology models Fathead Minnow Partially characterized genome High ecological/regulatory relevance Molecular markers, metabolomics Deterministic Model d CHOL = −v1 dt d PROG = v9 − v5 dt d 17 PROG = v 6 + v9 − v10 dt d DIONE = v10 + v7 − v11 − v12 dt d ESTRONE = v12 − v13 dt Small fish exposure system Fathead minnows d E 2 = v13 + v19 − v 20 dt PARAMETER ESTIMATION Objective function: where: d PREG = v1 − v 2 − v5 dt HYPOTHALAMIC-PITUITARY-GONADAL (HPG) AXIS HPG Axis Arterial blood   Conceptual Systems Model  Dopamine GABA taurine  5HTR Y2 R A B D1 R Brain, GnRH neuronal system NPY GnRH D2 R Venous blood d 17 PREG = v 2 − v3 − v 6 dt d DHA = v3 − v 4 − v7 dt d 19T = v18 − v19 dt d 11T = v14 − v15 dt f = ∑∑ [Si ,n − Si (t n ,θ )] I N i =1 n =1 2 I N = number of species (metabolites) = number of time samples = concentration of species (metabolite) = adjustable model parameters d KT = v15 − v16 dt Hypothalamus E2 T KT 5HT d DIOL = v 4 − v8 dt d T = v11 + v8 − v14 − v17 − v18 dt θ • • S Apply an iterative optimization algorithm Simultaneously estimate parameters for all dose concentrations GnRH Negative Feedback Inhibin Activin Pituitary, gonadotrophs Activin GnRH Follistatin PACAP NPY Enzyme Kinetics  GnRH R MODEL SIMPLIFICATION LH FSH Anterior Pituitary  Activin R PACAP R LHβ GPα Y1 R FSHβ D2 R GnRH R LH, FSH Gonads (Ovaries, Testes) VTG Outer mitochondrial membrane Preg 3β HSD Prog P450c17 (lyase) Dione P450 arom estradiol E2 E+S + I Ki Km ES E+P v (reaction rate) Vmax Vmax 2 Increasing inhibition Rate-limiting reaction Michaelis-Menten model P450scc Inner mitochondrial membrane Competitive inhibition P450c17 (hydroxylase) 17-prog 17βHSD EI • • Km Motivation StAR E2, T, KT Cholesterol 21-hydroxylase 11-deoxycortisol 20βHSD 20βS testosterone T • • • • More intuitive understanding of dynamic functional behavior Reduces number of parameters Identify rate limiting step(s): quasi-steady state approximations Identify preferred pathways P45011β Method Steroid hormone responsive tissues (e.g. liver, gonads) Feedback control system of the HPG axis that regulates synthesis and secretion of primary steroid hormones (estradiol (E2), testosterone (T), and 11-ketotestoterone (KT, only in male fish)) by the release of gonadotropin releasing hormone (GnRH) from the hypothalamus, and luteinizing hormone (LH) and follicle stimulating hormone (FSH) from the pituitary. Inhibin Activin LDL HDL LH FSH LDL R HDL R LH R FSH R Generalized gonad 11-testosterone 20βHSD 17α,20β-P (MIS) 11βHSD ketotestosterone S (substrate conc.) ACKNOWLEDGMENTS KT Mathematical Model NHEERL, U.S. EPA, Duluth, MN Gerald Ankley, PhD Dan Villeneuve, PhD E2 ERα,β1,β2 VTG ZRP Liver VTG ZRP v= Vmax S S + α Km I α = 1+ Ki DISCLAIMER This work was reviewed by the U.S. EPA and approved for publication but does not necessarily reflect Agency policy. Conceptual systems model shows key regulatory components of HPG axis. Green and red arrows indicate activation and negative feedback (inhibition), respectively. White boxes indicate proteins and peptides. Small molecules (e.g. steroids and neurotransmitters) are shown in italics. 3 parameters: V max , K m , K i

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