It’s actually not the skin itself but rather, the area just under the skin of fruits is the part of the fruit that is the most rich in nutrients. This is why when buying fresh fruits, consumers should avoid bruising because the chemical reactions that occur from bruising cause the loss of some nutrients. Also, when slicing, dicing, chopping and mashing fruits, this gets rid of some of the vitamins that fruits have by exposing the surfaces to air and light.
The skins also have an incredible value for fiber. Because the fruits and vegetables need to protect themselves, they form a tougher outer layer which is often fibrous. This is one reason that more of the nutritional value is in the skin. As far as why more of the antioxidants are in the skin (such as with grapes) it could be because the sun can cause oxidative damage through UV rays, and the fruit or vegetable needs to have a defense against this, so they have more antioxidants in the skins, but that is just a guess, I could not find anything saying why there are more nutrients in skins than the meats of fruits.
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