Infrared multiple photon dissociation spectroscopy of ciprofloxacin: Investigation of the protonation site

The vibrational spectrum of isolated protonated ciprofloxacin was recorded in the range 1100-2000 cm(-1) by means of infrared multiple photon dissociation (IRMPD) spectroscopy. The spectrum was obtained by electrospraying a methanol solution of ciprofloxacin in a Paul ion trap, coupled to the tunable IR radiation of a free electron laser. This spectroscopic study has been complemented by quantum chemical calculations at the DFT and MP2 levels of theory to identify the possible structures present under our experimental conditions. Several low-energy isomers with protonation occurring at the piperazinyl amino group and at the carbonyl group are predicted in the energy range 0-84 kJ mol(-1). A good agreement between the measured IRMPD spectrum and the calculated absorption spectrum is observed for the isomer protonated at the piperazinyl amino group. This isomer is calculated at MP2 level of theory to lie about 76 kJ/mol above the most stable isomer which is protonated at the quinone carbonyl group. This discrepancy can be rationalized by assuming that the protonation at the piperazinyl amino group, typical of the zwitterionic form that is found in protic solvents, is retained in the ESI process. The vibrational bands observed in the IRMPD spectrum are assigned to normal modes of the isomer protonated at the piperazinyl amino group, with deviations of less than 20 cm(-1) between measured and calculated frequencies. (C) 2011 Elsevier B.V. All rights reserved.