Actually, both starches and "complex carbs" are polysaccharides (long chains of sugar molecules). Starches are the most common carb in the human diet, and come from plant sources. Each type of starch contains a ratio of amylose to amylopectin, and depending on this ratio (as well as the arrangement and size of granules) will determine it's type. For example, potato starch has very large granules, where as rice starch has relatively small granules. Also, starches with high amylose are known to be used for their gel like, and adhesion properties in some industrial processing, and can be detrimental to health due to their resistant nature (resistant starch, a starch that resists digestion). Resistant starch is a whole other topic, but an example is when you let an already cooked potato become cool, you're allowing for a small percentage (I think maybe 6-7%) of it's starch to become resistant through the process wherein the amylose is leached out of the granules (after the semi-crystalline structure has been heated, it bursts or opens up, persay). Another example, ever left a sweet potato in the oven, even if on low heat, for a day or so? What happens to it? It becomes almost gelatin-like. Well, this is the same process I just described. It's the ability of water to bind to the granules that gives the starch viscosity (solubility through heat).
Anyway, not all starches are bad, and sweet potato happens to contain a more healthy version of starch for them most part. Keep in mind, gly***ic index when picking carbohydrate sources, and in relation to quantities, one should also factor in the gly***ic load, or insulin index. Hope this was informative.
I recommend Quinoa, which is actually a complete protein source as well, relatively low gly***ic, as well as not containing gluten (it's not a member of the grass family, it's actually a specific species of fruit [chenopod], however it's very grain-like in nature).
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