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MSG is a sodium salt of the amino acid called glutamic acid. (In water it dissolves into sodium and glutamate ions.) Free glutamate is an important neurotransmitter in the body and is also present in meaty-tasting foods, like parmesan cheese, soy sauce, steak sauce, and tomato sauce.
Commercial MSG is an extract of yeast, which produces almost entirely the L-glutamate form that is found in the human body, while bacterial fermentation (as in soy sauce) also produces some of the mirror-image molecules (D-glutamate) that do not enhance flavor.
Under extreme heat, glutamate curls up into pyroglutamate. (This is also sold as a nutritional substitute. Maybe some enterprising company decided that they could sell scorched MSG?). At some temperature above this, the pyroglutamate loses ammonia (NH3) and falls apart the rest of the way.
The thermal decomposition of glutamate occurs somewhere above 329F, just a bit less hot than the temperature at which melted butter starts to smoke. Like any burning organic matter, you shouldn't breathe the smoke, which could include harmful nitrogen oxides, carbon monoxide, and carbon dioxide. http://en.wikipedia.org/wiki/Glutamic_acid
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