An ability that triggers when something "attacks and isn't blocked" triggers in the declare blockers step after blockers are declared if (1) that creature is attacking and (2) no creatures are declared to block it. It will trigger even if that creature was put onto the battlefield attacking rather than having been declared as an attacker in the declare attackers step.

If multiple creatures block a creature with afflict, afflict triggers only once.

Afflict causes the defending player to lose life; it's not damage or combat damage.

If a creature is attacking a planeswalker, that planeswalker's controller is the defending player.

Afflict resolves before combat damage is dealt. If this loss of life brings a player to 0 life or less, that player loses the game immediately. A blocking creature with lifelink won't deal combat damage in time to save that player.