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Roast peppers directly over the flame of a gas-stove burner or under a broiler, turning often, until charred on all sides, about 5 minutes. Transfer to a plastic bag, and let stand 15 minutes. Peel peppers, and discard stems, seeds, and ribs. Tear flesh into thick strips.
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Heat a large cast-iron skillet over high heat. Generously season chops on both sides with salt and pepper. Brown chops on both sides, turning once, about 4 minutes total.
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Stir in garlic and capers, and cook 30 seconds, stirring to prevent garlic from burning. Add wine, and cook, stirring and scraping up browned bits as wine reduces to a glaze, about 3 minutes. Add roasted peppers.
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With pan still very hot, add vinegar, and cook 2 minutes, swirling skillet as vinegar bubbles. Reduce heat to medium. Cover, and cook until chops are cooked through and internal temperature reaches 138 degrees (they should be slightly pink inside), 4 to 5 minutes. Serve pork chops and peppers over polenta.