waiting for baked goods to cool down

Hi All. my brother in law is a wonderful baker. He always waits for his baked goods (breads, pies, cookies) to cool down before digging into them because, I think there is a scientifc reason, structure sets up better, something like that. I do not wait. Lately, I've been wondering - is it really that big a deal? why do people wait? Also, if you can't contain yourself, are there any goods that are ok to dig into hot, because you have no patience? obviously, pizza you can dig into right away, right? (well, I guess there's always the chance you can burn yourself if you wait only nanoseconds for the food)

 
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