Dipolar motions and ionic conduction in an ibuprofen derived ionic liquid.

It was demonstrated that the combination of the almost water insoluble active pharmaceutical ingredient (API) ibuprofen with the biocompatible 1-ethanol-3-methylimidazolium [C2OHMIM] cation of an ionic liquid (IL) leads to a highly water miscible IL-API with a solubility increased by around 5 orders of magnitude. Its phase transformations, as crystallization and glass transition, are highly sensitive to the water content, the latter shifting to higher temperatures upon dehydration. By dielectric relaxation spectroscopy the dynamical behavior of anhydrous [C2OHMIM][Ibu] and with 18.5 and 3% of water content (w/w) was probed from well below the calorimetric glass transition (Tg) up to the liquid state. Multiple reorientational dipolar processes were detected which become strongly affected by conductivity and electrode polarization near above Tg. Therefore [C2OHMIM][Ibu] exhibits mixed behavior of a conventional molecular glass former and an ionic conductor being analysed in this work through conductivity, electrical modulus and complex permittivity. The dominant process, σα-process, originates by a coupling between both charge transport and dipolar mechanisms. The structural relaxation times were derived from permittivity analysis and confirmed by temperature modulated differential scanning calorimetry. The temperature dependence of the ß-secondary relaxation is coherent with a Johari-Goldstein (ßJG) process as detected in conventional glass formers.

Confinement effects on the dynamic behavior of poly(D,L-lactic acid) upon incorporation in α-cyclodextrin.

Inclusion complexes (ICs) composed of α-cyclodextrin (α-CD) and poly(D,L-lactic acid) (PDLLA), with 10/24 (IC1) and 15/46 (IC2) (% w/w) of PDLLA incorporated/initial PDLLA weight percentage, were prepared and characterized mainly by dielectric relaxation spectroscopy (DRS). Bulk PDLLA was also analyzed for comparison. DRS was revealed to be a suitable tool to distinguish the dynamical response of the PDLLA regions constrained in between α-CD channels from the fraction incorporated inside channels. While the cooperative α-process undergoes a dramatic depletion shifting to higher temperatures (∼4.5 °C) for the PDLLA interchannels portion, it is suppressed for PDLLA chains inside pores. It was demonstrated that the broad secondary relaxation of bulk PDLLA is the Johari-Goldstein process (ßJG-process). The detection of its analogue in the ICs at higher frequencies, to a greater extent in IC1, is interpreted as a true confinement effect where the dimensions of the α-CD channels interfere with the length scale of the ßJG-process. The limit predicted in the framework of the coupling model, where the α-relaxation transforms in the ßJG-process, seems to be reached in the ICs. Furthermore, it was found that the length scale of the additional γ process only detected in the ICs is inferior to inter- or intrachannel dimensions.

Molecular mobility of amorphous S-flurbiprofen: a dielectric relaxation spectroscopy approach.

Amorphous S-flurbiprofen was obtained by the melt quench/cooling method. Dielectric measurements performed in the isochronal mode, conventional and temperature modulated differential scanning calorimetry (TMDSC) studies showed a glass transition, recrystallization, and melting. The different parameters characterizing the complex molecular dynamics of amorphous S-flurbiprofen that can have influence on crystallization and stability were comprehensively characterized by dielectric relaxation spectroscopy experiments (isothermal mode) covering a wide temperature (183 to 408 K) and frequency range (10(-1) to 10(6) Hz): width of the α-relaxation (ßKWW), temperature dependence of α-relaxation times (τα), fragility index (m), relation of the α-relaxation with the ß-secondary relaxation, and the breakdown of the Debye-Stokes-Einstein (DSE) relationship between the structural relaxation time and dc-conductivity (σdc) at deep undercooling close to Tg. The ß-relaxation, observed in the glassy as well as in the supercooled state was identified as the genuine Johari-Goldstein process, attributed to localized motions and regarded as the precursor of the α-relaxation as suggested in the coupling model. A separation of about 6 decades between the α- and ß-relaxation was observed at Tg; this decoupling decreased on increasing temperature, and both processes merged at Tαß = 295 K. The temperature dependence of the α-relaxation time, τα, was described by two Vogel-Fulcher-Tammann-Hesse equations, which intercept at a crossover temperature, TB = 290 K, close to the splitting temperature between the α- and ß-relaxation. From the low temperature VFTH equation, a Tg(DRS) = 265.2 was estimated (at τα =100 s) in good agreement with the calorimetric value (Tg,onset,TMDSC = 265.6 K), and a fragility or steepness index m = 113 was calculated allowing to classify S-flurbiprofen as a fragile glass former. The α-relaxation spectra were found to be characterized by a relatively large degree of nonexponentiality (ßKWW = 0.52). A breakdown of the DSE log10 σdc - log10 τ relation was observed revealing an enhancement of translational ionic motions in comparison with the orientational molecular motions as the glass transition temperature Tg is approached from above.

Real-time monitoring of molecular dynamics of ethylene glycol dimethacrylate glass former.

The isothermal cold-crystallization of the glass-former low-molecular-weight compound, ethylene glycol dimethacrylate (EGDMA), was monitored by real-time dielectric relaxation spectroscopy (DRS) and differential scanning calorimetry (DSC). The alpha-relaxation associated with the dynamic glass transition as detected by DRS was followed at different crystallization temperatures, T(cr), nearly above the glass transition temperature, 176 K (1.06 < or = T(cr)/T(g) < or = 1.12). It was found that the alpha-process depletes upon cold-crystallization with no significant changes in either shape or location. At advanced crystallization states, a new relaxation, alpha'-process, evolves that was assigned to the mobility of molecules lying adjacent to crystalline surfaces. From the time evolution of the normalized permittivity, it was possible to get kinetic information that was complemented with the calorimetric data. From DSC measurements that were also carried out under melt-crystallization, an enlarged temperature range was covered (up to T(cr)/T(g) = 1.24), allowing us to draw a diagram of time-temperature crystallization for this system. Dielectric relaxation spectroscopy proved to be a sensitive tool to probe the mobility in the remaining amorphous regions even at high crystallinities.

Dielectric characterization of neutralized and nonneutralized chitosan upon drying.

Isothermal dielectric loss spectra of neutralized and nonneutralized chitosan were acquired in successive runs from -130 degrees C up to increasing final temperatures, in a frequency range between 20 Hz and 1 MHz. Essentially, three relaxation processes were detected in the temperature range covered: (i) a beta-wet process, detected when the sample has a higher water content that vanishes after heating to 150 degrees C; (ii) a beta process, which is located at temperatures below 0 degrees C, becoming better defined and maintaining its location after annealing at 150 degrees C independently of the protonation state of the amino side group; and (iii) a sigma process that deviates to higher temperatures with drying, being more mobile in the nonneutralized form. Moreover, in dried neutralized chitosan, a fourth process was detected in the low frequency side of the secondary beta process that diminishes after annealing. Whether this process is a distinct relaxation of the dried polymer or a deviated beta-wet process due to the loss of water residues achieved by annealing is not straightforward. Only beta and sigma processes persist after annealing at 150 degrees C. The changes in molecular mobility upon drying of these two relaxation processes were evaluated.

Molecular motions in chitosan studied by dielectric relaxation spectroscopy.

Neutralized and nonneutralized chitosan films subject to different thermal treatments were studied by dielectric relaxation spectroscopy from -130 to +150 degrees C in the frequency range between 20 Hz and 1 MHz. Two main relaxation processes, both arrhenian type, were detected: process I at temperatures below 0 degrees C with a mean activation energy of 49 +/- 1 kJ mol(-1), which has the characteristics of a secondary relaxation process related with local chain dynamics, and process II observable at higher temperatures with an activation energy of 94 +/- 2 kJ mol(-1), correlated with dc conductivity, which is found in dried polysaccharides systems. Process I is always observed in neutralized chitosan, but it is strongly depleted in the wet nonneutralized form. Although the location of process I is independent of NH2/NH3+ side group, process II deviates to higher temperatures with dryness in both chitosan forms, being located at lower temperatures in nonneutralized chitosan.