Of these two quotes, the one that would best represent the point in the novel when Tom realizes that Daisy loves Gatsby would be the first, "You always look so cool." This quote is stated by Daisy when they (Tom, Daisy, Gatsby, Jordan, and Nick) go to the Biltmore Hotel in NYC toward the end of the novel. Daisy is complaining of how hot it is and then says, "You always look so cool", in reference to Gatsby.
Immediately following this, Tom becomes very upset and begins a verbal argument with Gatsby which blows up into a huge fight in which Tom reveals a great deal of information about Gatsby that was previously unknown to Daisy.
The second quote that you have ("You resemble the advertisement of the man") is said by Nick to the character known as "Owl Eyes" who he finds in Gatsby's library the first time he goes to one of Gatsby's parties.
No - Nick did NOT say that!