title: Molecular motions in amorphous ibuprofen as studied by broadband dielectric spectroscopy.
abstract: The molecular mobility of amorphous ibuprofen has been investigated by broadband dielectric relaxation spectroscopy (DRS) covering a temperature range of more than 200 K. Four different relaxation processes, labeled as alpha, beta, gamma, and D, were detected and characterized, and a complete relaxation map was given for the first time. The gamma-process has activation energy E a = 31 kJ.mol (-1), typical for local mobility. The weak beta-relaxation, observed in the glassy state as well as in the supercooled state was identified as the genuine Johari-Goldstein process. The temperature dependence of the relaxation time of the alpha-process (dynamic glass transition) does not obey a single VFTH law. Instead two VFTH regimes are observed separated by a crossover temperature, T B = 265 K. From the low temperature VFTH regime, a T g (diel) (tau =100 s) = 226 K was estimated, and a fragility or steepness index m = 93, was calculated showing that ibuprofen is a fragile glass former. The D-process has a Debye-like relaxation function but the temperature dependence of relaxation time also follows the VFTH behavior, with a Vogel temperature and a pre-exponential factor which seem to indicate that its dynamics is governed by the alpha-process. It has similar features as the Debye-type process observed in a variety of associating liquids, related to hydrogen bonding dynamics. The strong tendency of ibuprofen to form hydrogen bonded aggregates such as dimers and trimers either cyclic or linear which seems to control in particular the molecular mobility of ibuprofen was confirmed by IR spectroscopy, electrospray ionization mass spectrometry, and MD simulations.
authors.affiliation: Requimte, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
authors.forename: Ana R
authors.initials: AR
authors.lastname: Brás
authors.forename: João P
authors.initials: JP
authors.lastname: Noronha
authors.forename: Alexandra M M
authors.initials: AM
authors.lastname: Antunes
authors.forename: Maria M
authors.initials: MM
authors.lastname: Cardoso
authors.forename: Andreas
authors.initials: A
authors.lastname: Schönhals
authors.forename: Frédéric
authors.initials: F
authors.lastname: Affouard
authors.forename: Madalena
authors.initials: M
authors.lastname: Dionísio
authors.forename: Natália T
authors.initials: NT
authors.lastname: Correia
mesh_terms: D002152:Calorimetry, Differential Scanning; D002851:Chromatography, High Pressure Liquid; D004553:Electric Conductivity; D006860:Hydrogen Bonding; D007052:Ibuprofen / Q000737:chemistry*; D008958:Models, Molecular; D009038:Motion; D021241:Spectrometry, Mass, Electrospray Ionization; D013055:Spectrophotometry, Infrared; D013057:Spectrum Analysis / Q000379:methods*; D013696:Temperature
chemical_list: D007052:Ibuprofen