In addition to blood vessels, vein is used to describe things such as wood, metal ore, and ribs in a leaf.
Vain is used to describe people who seem to be full of themselves and are viewed as "empty." It can also be used for an act that didn't quite go as planned, so it was "done in vain."
Vane is usually used in reference to a weather vane, but it can also refer to a blade.
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