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Because the hiragana ends with an う sound, you know this word is a verb. The kanji itself means punch, so the verb means to punch, to strike, or to hit.
Someone is nagging (なぐ) you and nagging you about something. You can't take it any more, so you turn around to punch them in the face.
ゴングが鳴った瞬間、そのボクサーは相手の顎を思い切り殴り付けた。
The moment the gong sounded, the boxer punched his opponent's jaw with all his strength.
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