Secondary Relaxation Research Articles

Study of the molecular mobility of (±)-methocarbamol in the amorphous solid state

The experimental techniques of differential scanning calorimetry (DSC) and thermally stimulated depolarization currents (TSDC) were used to study the thermal behavior of the pharmaceutical drug (±)-methocarbamol and its slow molecular mobility (in the 10−3–10−2 Hz range) in the amorphous solid state. The possibility of polymorphism was considered based on the DSC results. The glass forming ability and the glass stability were investigated by DSC, and the general kinetic features of the main relaxation, including the fragility or steepness index, were studied by both experimental techniques. The secondary relaxations detected by TSDC revealed fast and slow (Johari-Goldstein) modes. These secondary relaxations of different nature were assigned based on physical aging studies.

Thermomechanical and large deformation behaviors of antiplasticized epoxy resins: Effect of material formulation and network architecture

A series of amine‐hardened epoxies were prepared by systematically varying the stoichiometric ratio and the relative amounts of diepoxide and monoepoxide resin to chemically control the material composition and macromolecular architecture (chain segments flexibility; crosslink density; amounts of dangling groups). Positron Annihilation Lifetime Spectroscopy was used to investigate the free volume associated to the various epoxy formulations, while dynamic‐mechanical analysis was employed to investigate their network density and their primary and secondary mechanical relaxations. The mechanical behavior at small and large strain was studied by means of tensile and compression tests. The results pointed out that deviations from the ideal stoichiometric composition and the addition of monoepoxide resins lead to significant room temperature stiffening, together with a reduction of the crosslink density and glass transition temperature. This behavior, phenomenologically associated to antiplasticization, was interpreted according to the specific macromolecular architecture and ascribed to chain mobility hindrance, as revealed by secondary transitions, whereas no significant contribution from the free volume could be evidenced. Furthermore, it was shown that depending on the strain scale and on the corresponding deformational mechanisms, the mechanical response may be differently influenced either by the presence of dangling groups or by the network density. POLYM. ENG. SCI., 57:553–565, 2017. © 2017 Society of Plastics Engineers

Dielectric relaxations in phosphoric acid‐doped poly(2,5‐benzimidazole) and its composite membranes

ABSTRACTPoly(2,5‐benzimidazole) (ABPBI)—a promising high‐temperature polymer electrolyte membrane—is characterized over a wide range of temperature (−50 to 220 °C) using broadband dielectric spectroscopy (BDS) to understand the various relaxation processes. The undoped ABPBI membrane shows two major secondary relaxations and a primary α relaxation. The effect of phosphoric acid (PA) and phosphotungstic acid grafted zirconium dioxide (PWA/ZrO2) nanoparticles on the chain relaxation and the proton conductivity is investigated. The phosphoric acid alters the relaxation trends, increases the number of free ions in the polymer matrix, and therefore the conductivity. The shift in the peak frequencies of different chain relaxation processes in the presence of PA and PWA/ZrO2 is attributed to the increase in free volume and the consequent easy motion of the polymer chains. The Fourier transform infra‐red (FTIR) spectroscopy of ABPBI and the acid‐doped composites show all the relevant peaks corresponding to CC, CN stretching, and phosphoric acid/phosphates, confirming the formation of ABPBI and doping with PA. The proton conductivity of the membranes is estimated from electrochemical impedance spectroscopy (EIS). To establish the effect of change in crystallinity on relaxations and proton conductivity, the undoped and PA‐doped membranes are characterized using thermogravimetric analysis and in situ XRD at high temperatures. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44867.

The Nature of Secondary Relaxations: The Case of Poly(ethylene-alt-propylene) Studied by Dielectric and Deuteron NMR Spectroscopy

Main (α-) and secondary (β-) relaxation of the linear poly(ethylene-alt-propylene) (PEP) with different molar masses are investigated by dielectric and 2H NMR spectroscopy. Regarding the α-process, time constants in the range 10–11–1 s are reported, and the correlation function is described by a Cole–Davidson function with stretching parameter β ≅ 0.34. Both methods show clear evidence of a pronounced β-process; the latter is thoroughly studied by different NMR techniques. The results are compared to toluene-d3 and toluene-d5, respectively, as reference systems. The solid-echo spectra as well as the spin–lattice relaxation display typical features of spatially highly restricted angular displacements similar to those reported in other glass-formers showing a β-process−like toluene. Above Tg all chain segments participate. As both chain and methyl group were deuterated and as the β-process is rather fast, its angular displacement growing with temperature above Tg is directly reflected in a reduction of the ...

Relaxation behavior of polyurethane networks with different composition and crosslinking density

The relaxation behavior of a series of solvent free polyurethane model networks with variable cross-link density prepared based on different commercial diols and a diisocyanate containing component are studied by differential scanning calorimetry (DSC), dynamic-mechanical analysis (DMA) and dielectric relaxation spectroscopy (DRS). A systematic decrease of the calorimetric glass temperature Tg as well as of the softening temperatures TαDMA and TαDRS from relaxation methods is observed with increasing length of the diol sequences between neighbored diisocyanate units acting as cross-linker. This trend is explained based on an internal plasticization of the polymeric network by long, highly mobile diol units containing an increasing fraction of methylene sequences. Cold crystallization effects are only indicated for the longest diol sequence under investigation. This is understood as a consequence of a large fraction of methylene sequences in combination with weaker geometrical constraints. Two secondary relaxations, β and γ, are observed in the glassy state for all amorphous samples at low temperatures by dielectric spectroscopy indicating the existence of localized motions in the polyurethane networks. Below Tg these relaxation processes are practically unaffected by changes in the length of the diol units and the softening behavior of the polymeric model networks. Interrelations between secondary β relaxation and cooperative α dynamics are indicated. An onset of the dielectric α relaxation strength Δεα is observed for all amorphous polyurethane networks. A linear extrapolation of Δεα vs. 1/T gives onset temperatures Ton which are in good agreement with αβ crossover temperatures Tαβ being the temperature where the difference between α and β relaxation times τα−τβ approaches a minimum. This finding supports an onset of the cooperative α motions in the αβ crossover region as reported in the previous literature for many other glass forming materials.

The bifunctional effect of propofol on thromboxane agonist (U46619)-induced vasoconstriction in isolated human pulmonary artery.

Propofol is known to cause vasorelaxation of several systemic vascular beds. However, its effect on the pulmonary vasculature remains controversial. In the present study, we investigated the effects of propofol on human pulmonary arteries obtained from patients who had undergone surgery. Arterial rings were mounted in a Multi-Myograph system for measurement of isometric forces. U46619 was used to induce sustained contraction of the intrapulmonary arteries, and propofol was then applied (in increments from 10–300 µM). Arteries denuded of endothelium, preincubated or not with indomethacin, were used to investigate the effects of propofol on isolated arteries. Propofol exhibited a bifunctional effect on isolated human pulmonary arteries contracted by U46619, evoking constriction at low concentrations (10–100 µM) followed by secondary relaxation (at 100–300 µM). The extent of constriction induced by propofol was higher in an endothelium-denuded group than in an endothelium-intact group. Preincubation with indomethacin abolished constriction and potentiated relaxation. The maximal relaxation was greater in the endothelium-intact than the endothelium-denuded group. Propofol also suppressed CaCl2-induced constriction in the 60 mM K+-containing Ca2+-free solution in a dose-dependent manner. Fluorescent imaging of Ca2+ using fluo-4 showed that a 10 min incubation with propofol (10–300 µM) inhibited the Ca2+ influx into human pulmonary arterial smooth muscle cells induced by a 60 mM K+-containing Ca2+-free solution. In conclusion, propofol-induced arterial constriction appears to involve prostaglandin production by cyclooxygenase in pulmonary artery smooth muscle cells and the relaxation depends in part on endothelial function, principally on the inhibition of calcium influx through L-type voltage-operated calcium channels.

The origin of the Debye relaxation in liquid water and fitting the high frequency excess response.

We critically review the literature on the Debye absorption peak of liquid water and the excess response found on the high frequency side of the Debye peak. We find a lack of agreement on the microscopic phenomena underlying both of these features. To better understand the molecular origin of Debye peak we ran large scale molecular dynamics simulations and performed several different distance-dependent decompositions of the low frequency dielectric spectra, finding that it involves processes that take place on scales of 1.5-2.0 nm. We also calculated the k-dependence of the Debye relaxation, finding it to be highly dispersive. These findings are inconsistent with models that relate Debye relaxation to local processes such as the rotation/translation of molecules after H-bond breaking. We introduce the spectrumfitter Python package for fitting dielectric spectra and analyze different ways of fitting the high frequency excess, such as including one or two additional Debye peaks. We propose using the generalized Lydanne-Sachs-Teller (gLST) equation as a way of testing the physicality of model dielectric functions. Our attempts at fitting the experimental spectrum using the gLST relation as a constraint indicate that the traditional way of fitting the excess response with secondary and tertiary Debye relaxations is problematic. All of our work is consistent with the recent theory of Popov et al. (2016) that Debye relaxation is due to the migration of Bjerrum-like defects in the hydrogen bond network. Under this theory, the mechanism of Debye relaxation in liquid water is similar to the mechanism in ice, but the heterogeneity and power-law dynamics of the H-bond network in water results in excess response on the high frequency side of the peak.

Dielectric Spectroscopy in Ibuprofen-Dioxane Mixture

In recent years, the dielectric study of amorphous pharmaceuticals has made a considerable effort towards correlating the molecular mobility with their physical and chemical stability. The molecular mobility of amorphous materials is affected by temperature, additives (such as water) and specific interactions (such as Hydrogen bond). Therefore, to understand the physicochemical instability of amorphous materials, nature of their molecular mobility needs to comprehend. In this order, the Dielectric and Calorimetric measurements were performed on a mixture of ibuprofen and 1,4-dioxane. The dielectric spectroscopy reveals two relaxation processes, (designated as αD, and α) in the supercooled region. The spectral shape of αD and α process can be explained satisfactorily throughout the frequency range using Havriliak-Negami (HN) shape function. The αD process is found to be Debye-like (i.e., αHN=0 and βHN=1) in nature and α process kinetically freezes at Tg-onset (DSC) implies that α- process indeed corresponds to the glass transition event. Both processes are found to be non-Arrhenius in nature. In addition, two secondary relaxation processes (designated as βJG and β) are observed and are comparable with the literature. The activation energy of β process indicates that it‟s originating from the fluctuations of the side group larger than -OH group. Also, the calculated fragility index demonstrates that ibuprofen is a fragile glass former.

Effect of secondary relaxation transitions on photo-induced anisotropy in glassy azobenzene-functionalized polymers

The β-relaxation transition in side-chain azobenzene-functionalized amorphous polymers can be directly found from the temperature behavior of infrared dichroism.

Amorphous physics and materials: Secondary relaxation and dynamic heterogeneity in metallic glasses: A brief review**Project supported by the National Natural Science Foundation of China (Grant Nos. 51401192 and 51611130120), the Natural Science Foundation of Shaanxi Province, China (Grant No. 2016JM5009), and the Fundamental Research Funds for the Central Universities of China (Grant Nos. 3102015ZY027 and 3102015BJ(II)JGZ019), the Aeronautical Science Foundation

Understanding mechanical relaxation, such as primary (α) and secondary (β) relaxation, is key to unravel the intertwined relation between the atomic dynamics and non-equilibrium thermodynamics in metallic glasses. At a fundamental level, relaxation, plastic deformation, glass transition, and crystallization of metallic glasses are intimately linked to each other, which can be related to atomic packing, inter-atomic diffusion, and cooperative atom movement. Conceptually, β relaxation is usually associated with structural heterogeneities intrinsic to metallic glasses. However, the details of such structural heterogeneities, being masked by the meta-stable disordered long-range structure, are yet to be understood. In this paper, we briefly review the recent experimental and simulation results that were attempted to elucidate structural heterogeneities in metallic glasses within the framework of β relaxation. In particular, we will discuss the correlation among β relaxation, structural heterogeneity, and mechanical properties of metallic glasses.

A new secondary relaxation in the rigid and planar 1-methylindole: Evidence from binary mixture studies.

Found in our recent dielectric study of a planar and rigid glass-former, 1-methylindole (1MID), is an unusual secondary relaxation unrelated in its dynamic properties to the structural α-relaxation. We speculated that it originates from the in-plane motion of the molecules, and the supposedly universal Johari-Goldstein (JG) β-relaxation with strong connection to the structural α-relaxation in rigid glass-formers is not resolved [X. Q. Li et al. J. Chem. Phys. 143, 104505 (2015)]. In this work, dielectric measurements are performed in binary mixtures of 1MID with two aromatics of weak polarity, ethylbenzene (EB) and triphenylethylene (TPE), in the highly viscous regimes near glass transition. EB and TPE have smaller and larger molecular sizes and glass transition temperatures Tg than 1MID, respectively. Strikingly, the results show that the resolved secondary relaxations of 1MID in the two mixtures share the same relaxation time and their temperature dependence as pure 1MID, independent of the mode and degree of dilution. The results indicate that the unusual secondary relaxation is not directly coupled with the α-relaxation, and support the in-plane-rotation interpretation of its origin. On the other hand, the supposedly universal and intermolecular JG β-relaxation coming from the out-of-plane motion of the planar molecule has weaker dielectric strength, and it cannot be resolved from the more intense in-plane-rotation secondary relaxation because the dipole moment of 1MID lies on the plane.

Relaxation processes in an aromatic polyamide-imide and composites on its basis with hydrosilicate nanoparticles

Features of the relaxation behavior of an aromatic polyamide-imide and a composite with nanotubes of magnesium silicate with the structure of chrysotile have been studied by dynamic mechanical analysis, dielectric spectroscopy, and differential scanning calorimetry. Two secondary relaxation (β1 and β2) transitions have been found, the activation energies of these processes have been determined, and the solvent effect on the cooperativeness degree has been studied. Changes in the value of the apparent activation energy of the β1-process caused by the subsequent heating of polymeric and composite samples have been analyzed according to the Starkweather procedure. It has been shown that, as the solvent is released from the polyamide-imide film, the polymer exhibits increasing local mobility, which are predetermined by the structure of the molecular unit. Using the GAMESS software, we have assumed the most probable dimer conformations that correspond to two repeating units of the polyamide-imide molecule.

Dielectric Relaxation Study at Ambient and Elevated Pressure of the Modeled Lipophilic Drug Fenofibrate.

We have investigated the molecular dynamics in supercooled liquid and glassy state of the pharmaceutical agent fenofibrate. To do that, dielectric relaxation studies at ambient and elevated pressure were performed. Data collected at atmospheric pressure were found to be in good agreement with that already reported in the literature. High-pressure studies enable us to distinguish the secondary relaxation processes of the different molecular origin. This includes (i) pressure insensitive γ-relaxation of the activation energy Ea = 28 kJ/mol and (ii) β-relaxation that senses the density increase and originates most probably from the intermolecular movements (Ea = 77 kJ/mol at 480 MPa). The results of high-pressure studies have also revealed the validity of isochronal superposition and decoupling between α-relaxation and translational motions of charged species reflected by dc conductivity. The latter one was found to intensify with increasing pressure. Finally, we also show that the presence of quite complex inter- and intramolecular hydrogen bonds might still exert some subtle effect on the molecular dynamics of supercooled fenofibrate.

The Slow Relaxation Dynamics in the Amorphous Pharmaceutical Drugs Cimetidine, Nizatidine, and Famotidine

The slow molecular mobility in the amorphous solid state of 3 active pharmaceutical drugs (cimetidine, nizatidine, and famotidine) has been studied using differential scanning calorimetry and the 2 dielectric-related techniques of dielectric relaxation spectroscopy and thermally stimulated depolarization currents. The glass-forming ability, the glass stability, and the tendency for crystallization from the equilibrium melt were investigated by differential scanning calorimetry, which also provided the characterization of the main relaxation of the 3 glass formers. The chemical instability of famotidine at the melting temperature and above it prevented the preparation of the amorphous for dielectric studies. In contrast, for cimetidine and nizatidine, the dielectric study yielded the main kinetic features of the α relaxation and of the secondary relaxations. According to the obtained results, nizatidine displays the higher fragility index of the 3 studied glass-forming drugs. The thermally stimulated depolarization current technique has proved useful to identify the Johari–Goldstein relaxation and to measure τβJG in the amorphous solid state, that is, in a frequency range which is not easily accessible by dielectric relaxation spectroscopy.

Effect of adding nanometre-sized heterogeneities on the structural dynamics and the excess wing of a molecular glass former.

We present the relaxation dynamics of glass-forming glycerol mixed with 1.1 nm sized polyhedral oligomeric silsesquioxane (POSS) molecules using dielectric spectroscopy (DS) and two different neutron scattering (NS) techniques. Both, the reorientational dynamics as measured by DS and the density fluctuations detected by NS reveal a broadening of the α relaxation when POSS molecules are added. Moreover, we find a significant slowing down of the α-relaxation time. These effects are in accord with the heterogeneity scenario considered for the dynamics of glasses and supercooled liquids. The addition of POSS also affects the excess wing in glycerol arising from a secondary relaxation process, which seems to exhibit a dramatic increase in relative strength compared to the α relaxation.

Influence of crystallinity on the dielectric relaxations of poly(butylene succinate) and poly[(butylene succinate)-co-(butylene adipate)

Amorphous and semi-crystalline poly(butylene succinate) (PBS) and poly[(butylene succinate)-co-(butylene adipate)] (PBSA) are studied with Differential Scanning Calorimetry and Broadband Dielectric Spectroscopy (BDS). It was shown that 21mol% of butylene adipate group decreases drastically the degree of crystallinity and the size of the crystal lamellae of the PBSA. For the two semi-crystalline polymers, the microstructure is well described by a three-phase model including a small degree of rigid amorphous fraction. Fragility indexes of the main dielectric relaxation are identical for each sample which shows similar segmental dynamics of their amorphous phase. BDS allows detecting complex secondary relaxations in semi-crystalline PBS and PBSA. Local motions are impacted by the microstructure and a new relaxation occurs in more constrained amorphous environments. Correlations between molecular mobility and barrier properties are proposed.

The Neurite Outgrowth Inhibitory Nogo-A-Δ20 Region Is an Intrinsically Disordered Segment Harbouring Three Stretches with Helical Propensity.

Functional recovery from central neurotrauma, such as spinal cord injury, is limited by myelin-associated inhibitory proteins. The most prominent example, Nogo-A, imposes an inhibitory cue for nerve fibre growth via two independent domains: Nogo-A-Δ20 (residues 544–725 of the rat Nogo-A sequence) and Nogo-66 (residues 1026–1091). Inhibitory signalling from these domains causes a collapse of the neuronal growth cone via individual receptor complexes, centred around sphingosine 1-phosphate receptor 2 (S1PR2) for Nogo-A-Δ20 and Nogo receptor 1 (NgR1) for Nogo-66. Whereas the helical conformation of Nogo-66 has been studied extensively, only little structural information is available for the Nogo-A-Δ20 region. We used nuclear magnetic resonance (NMR) spectroscopy to assess potential residual structural propensities of the intrinsically disordered Nogo-A-Δ20. Using triple resonance experiments, we were able to assign 94% of the non-proline backbone residues. While secondary structure analysis and relaxation measurements highlighted the intrinsically disordered character of Nogo-A-Δ20, three stretches comprising residues 561EAIQESL567, 639EAMNVALKALGT650, and 693SNYSEIAK700 form transient α-helical structures. Interestingly, 561EAIQESL567 is situated directly adjacent to one of the most conserved regions of Nogo-A-Δ20 that contains a binding motif for β1-integrin. Likewise, 639EAMNVALKALGT650 partially overlaps with the epitope recognized by 11C7, a Nogo-A-neutralizing antibody that promotes functional recovery from spinal cord injury. Diffusion measurements by pulse-field gradient NMR spectroscopy suggest concentration- and oxidation state-dependent dimerisation of Nogo-A-Δ20. Surprisingly, NMR and isothermal titration calorimetry (ITC) data could not validate previously shown binding of extracellular loops of S1PR2 to Nogo-A-Δ20.

Dynamical and orientational structural crossovers in low-temperature glycerol.

Mean-square displacements of hydrogen atoms in glass-forming materials and proteins, as reported by incoherent elastic neutron scattering, show kinks in their temperature dependence. This crossover, known as the dynamical transition, connects two approximately linear regimes. It is often assigned to the dynamical freezing of subsets of molecular modes at the point of equality between their corresponding relaxation times and the instrumental observation window. The origin of the dynamical transition in glass-forming glycerol is studied here by extensive molecular dynamics simulations. We find the dynamical transition to occur for both the center-of-mass translations and the molecular rotations at the same temperature, insensitive to changes of the observation window. Both the translational and rotational dynamics of glycerol show a dynamic crossover from the structural to a secondary relaxation at the temperature of the dynamical transition. A significant and discontinuous increase in the orientational Kirkwood factor and in the dielectric constant is observed in the same range of temperatures. No indication is found of a true thermodynamic transition to an ordered low-temperature phase. We therefore suggest that all observed crossovers are dynamic in character. The increase in the dielectric constant is related to the dynamic freezing of dipolar domains on the time scale of simulations.

Interrelationships Between Structure and the Properties of Amorphous Solids of Pharmaceutical Interest

This commentary explores fundamental issues associated with the structure of amorphous solids of pharmaceutical interest in terms of the effects of such structure on: various thermodynamic properties; the glass transition temperature, Tg, physical aging of glasses, polyamorphism; molecular mobility by primary diffusive and secondary Johari-Goldstein relaxations; solid-state crystallization; water vapor absorption; and the formation of active pharmaceutical ingredients–polymer dispersions. Recognizing that small organic molecules, as well as polymers used pharmaceutically, tend to exhibit highly “fragile” behavior in the supercooled liquid state, that is, significant increases in relaxation time or viscosity with decreasing temperature as Tg is approached, particular emphasis has been placed on local and global structural factors, that appear to give rise to the nonexponential dependence of the structural relaxation time and viscosity associated with spatial and temporal heterogeneity, at temperatures below the “crossover temperature,” Tx, (1.2-1.4 Tg), using theoretical random close packing and “jamming” models. Utilizing a “2-region” structural model of the glassy state, wherein glasses consist of clustered domains surrounded by a higher energy and less dense “microstructure,” it has been possible to better understand the underlying structural factors that give rise to a number of important phenomena which occur in the glassy state.

Main and secondary relaxations in an Au-based bulk metallic glass investigated by mechanical spectroscopy

The dynamic mechanical relaxation behavior of an Au49Cu26.9Si16.3Ag5.5Pd2.3 (at.%) bulk metallic glass was investigated by mechanical spectroscopy as a function of temperature or driving frequency. The mechanical spectra show the evidence of a secondary relaxation (or β) process at low temperature or high driving frequency. The main relaxation (α) is clearly evident at higher temperature or lower frequency. Crystallization induces an increase in elastic modulus, in two steps, which correspond to the formation of two different crystalline phases, as determined by in-situ X-ray diffraction experiments. Master curves could be obtained based on the time-temperature superposition principle. From these curves the apparent activation energies for the two relaxation phenomena were determined: Eβ = 1.10 eV and Eα = 3.65 eV, respectively. These values indicate that the secondary relaxation may be attributed to local atomic movements, while the α relaxation corresponds to correlated movements.