Subject line pretty much says it all, but I'll try to elaborate. Line of effect/sight rules are all written in terms of spell effects, not supernatural effects.
So, for instance, a witch has already successfully Misfortuned an enemy but is then cut off from the enemy by say a Wall of Stone spell so that s/he has absolutely no line of effect to the Mistfortuned enemy, but is still within 30 feet of said enemy. Can s/he Cackle to extend duration of said Misfortune?
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Line of effect applies to everything and pretty much says what it means. If there is no line of effect, then you cannot affect.
Cackle doesn't require picking targets, so line of sight doesn't apply. There was a thread a while back debating whether cackle required you to hear the witch, or the witch to make a sound, but I don't recall if that was ever resolved.
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Witch, Cackle Hex: Does my character literally have to cackle madly when I use this hex, or is that just flavor text?
Your character actually has to cackle—probably in a strong voice, akin to the volume and clarity necessary for verbal spell components.
Edit 7/19/13:
If the witch is in a silence effect, she can't use the cackle hex.
If the target is in a silence effect, it is unaffected by the cackle.
This may require some clarifying text in the next printing of the Advanced Player's Guide.—Pathfinder Design Team, 06/06/13
"If the target is in a silence effect, it is unaffected by the cackle."
That make me think that the target need to hear the witch cackle for it to work.