Can intelligent humanoid familiars use item on its master?
EX: Sprites, Homunculus and the like
Can they use/apply potions to their injured master, or use a wand of cure wounds on them?
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A familiar needs to be able to manipulate the magic item. Since they are humanoid and have hands, they can if the item is of a size they can handle.
It has the same skill ranks as the master, but uses its own modifiers, including class skill. Class skills for familiars are only Acrobatics, Climb, Fly, Perception, Stealth, and Swim (before any archetype or feature modifies the list).
If it is a wand, the familiar must be able to speak the command word too.
For some items like wands, it will need to make a UMD test, like any other character.