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Can you make an unarmed strike and still gain the +2 AC from Dueling Mastery?
Benefit: You gain a +2 bonus on Initiative checks as long as you start combat with a dueling sword in your hand. As long as you wield only a single dueling sword in one hand, you gain a +2 shield bonus to your AC—if you wield the sword in two hands, this bonus drops to a +1 shield bonus to AC.Mostly I'm thinking as an AoO.
Difficult to know the RAW answer as the term "wield" is not well-defined and used in ways that illicit argument on the boards.
Although it can be argued that you are "wielding" your arm or leg that makes the AOO (thus negating the feat), I would allow it for no other reason than I like the image of the swashbuckling duelist who punches and kicks his foes in battle. Watch any Errol Flynn movie or the 1974 Three Musketeers.
I would say this is probably a bit like using a defending weapon.
Then there is this FAQ:
Defending Weapon Property: Do I have to make attack rolls with the weapon to gain its AC bonus?
Yes. Merely holding a defending weapon is not sufficient. Unless otherwise specified, you have to use a magic item in the manner it is designed (use a weapon to make attacks, wear a shield on your arm so you can defend with it, and so on) to gain its benefits.
Therefore, if you don't make an attack roll with a defending weapon on your turn, you don't gain its defensive benefit.
Likewise, while you can give a shield the defending property (after you've given it a +1 enhancement bonus to attacks, of course), you wouldn't get the AC bonus from the defending property unless you used the shield to make a shield bash that round--unless you're using the shield as a weapon (to make a shield bash), the defending weapon property has no effect.
I would say you would need to make at least one attack with it each round to gain the benefit to AC. The initiative benefit will always be there.