u/Red_AtNight isn’t quite right here. They are correct that starch is the key, but what it’s doing is absorbing water in a process called ‘gelatinization’. Yes, the start molecules are chemically changing their structures and this cannot be undone, but the starch is not being decomposed to simple sugars, it remains a ‘complex carbohydrate’. To be a bit more specific, the starch compounds in a potato are arranged in a structure called ‘grains’ and each variety of potato has slightly different grain set ups which is why some potatoes are better, or worse for baking vs. mashing vs. frying etc.
What u/Red_AtNight is talking about is based on a real concept though. Starch is made up a huge number of tiny sugar molecules. To humans starches don’t taste ‘sweet’ but our saliva does contain a digestive chemical called “Salivary Amylase” which hits carbohydrates like a wood chipper and rips them in their tiny sugars *and that* is why a cooked potato will taste sweet on the tongue, because your saliva has already started digesting it, like a Xenomorph watching redshirts make out in a shower stall.
Fun Fact: Many cultures that lacked Europe’s access to grains relied on salivary amylase to pre-digest starches for fermenting. People would literally sit in a circle, take big bites of starchy roots and foods, chew chew chew and then spit the mush into a big pot as a group. The salivary amylase would convert the starch to sugar and allow it to be fermented. Next time you take a sip of a generic light lager and wonder to your self “how the fuck did *this* become the go-to beer for the world?” remember what people were drinking *prior* to the great German diaspora.
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