If it had been 114 one-dollar bills, non-issue. Store takes the money and moves on. The probable cause test here has to be to the police that detained him. I assume the probable cause test is subjective, so if the cop is ignorant in matters of currency, and is honestly fooled into belief he has a perp passing counterfeit currency, then he has probable cause. A belief based on a mistake, to be sure.
If ignorance of the law is no excuse for private citizens, it likewise shouldn't be an allowable excuse for police officers.