You never want to put any water based liquids into your pan before cooking meat or veg, so long as you have water boiling you will never be cooking above 100°C (212°F) as the water will use up any excess energy so you will never reach browning or caramelization, as well as that odor molecules are not water soluble so you will be letting a lot of flavour escape, that's why most recipes call for aromatic veg (onion, garlic, carrots, celery) and meats to be cooked in a little fat first. You'll never cook away any sweetness either, reductions intensify flavour, not diminish them.
It's certainly an interesting dish though and I've only just purchased a slow cooker so I'll be looking for things to try. A good cheap eye of round is somewhere on top of that list.
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