Chain Relaxation Processes Research Articles

Drug Delivery System Based on Carboxymethyl Cellulose Containing Metal-Organic Framework and Its Evaluation for Antibacterial Activity.

A novel drug delivery system based on carboxymethyl cellulose containing copper oxide at melamine and zinc oxide at melamine framework (CMC-Cu-MEL and CMC-Zn-MEL) was prepared by the hydrothermal route. Synthesized nanocomposites were characterized by FTIR, SEM, and Raman spectroscopy. In addition, transmission electron microscopy (TEM) and selected area electron diffraction (SAED) images were applied to confirm the particle size and diffraction pattern of the prepared nanocomposites. Furthermore, the crystallinity of the synthesized CMC, CMC-Cu-MEL, and CMC-Zn-MEL materials was studied via X-ray diffraction (XRD). Estimating the transport exponent, which discloses the solvent diffusion and chain relaxation processes, and the Ritger–Peppas kinetic model theory were used to control the TC release mechanism from CMC-Cu-MEL and CMC-Zn-MEL. Additionally, the CMC-Cu-MEL and CMC-Zn-MEL containing TC had the highest activity index percents of 99 and 106% against S. aureus and 93 and 99% against E. coli, respectively. The tailored CMC-Cu-MEL and CMC-Zn-MEL for drug delivery systems are expected to be feasible and efficient.

Fabrication of Chitosan Nanofibers Containing Some Steroidal Compounds as a Drug Delivery System.

A novel drug delivery system based on chitosan nanofibers containing some steroidal derivatives was developed using an electrospinning process. Oxazolines and aziridines from the cholestane series of steroidal epoxides were successfully synthesized and characterized by elemental analysis, Fourier transforms infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1HNMR), and mass spectroscopy (MS). Steroidal-compound-loaded chitosan (ST-CH) nanofibers were fabricated using the electrospinning technique in the presence of polyvinylpyrrolidone (CH/PVP). The electrospun nanofibers were characterized by scanning electron microscopy (SEM). The swelling degree of the electrospun nanofibers and their steroidal compound release performance were studied as well. Furthermore, their antibacterial activity against gram-positive (Staphylococcus aurous) and gram-negative bacteria (Escherichia coli) was evaluated. The experimental data revealed that identical and bead-free nanofiber mats loaded with 10 Wt. % of synthesized steroidal derivatives had been obtained. The FTIR spectrum proved that no change occurred in the chitosan structure during the electrospinning process. The synthesized nanofiber mats showed a high swelling degree and a burst release of steroidal compounds after 2 h doping in phosphate buffer saline. In addition, the electrospun nanofibers containing 3β-chloro-N-amido-5α-cholestano-aziridine and those containing 3β-acetoxy-N-amido-5α-cholestano-aziridine were the most active, with activity indices of 91 and 104% in the case of S. aureus and 52% and 61% in the case of E. coli, respectively. The release mechanism by CH/PVP of the drug samples was studied based on the charge density and diffusion controlled factors. The oxazoline derivatives release mechanism from CH/PVP was evaluated by applying the suppositions of the Ritger-Peppas kinetic model and by estimating the transport exponent; the latter revealed the involvement of the solvent diffusion and chain relaxation processes. Tailored steroidal loaded-chitosan (ST-CH) nanofibers are expected to be feasible and efficient drug delivery systems.

Flow-induced crystalline precursors in entangled Poly(vinyl alcohol) aqueous solutions

Flow-induced formation of crystalline precursors was systematically investigated for entangled poly (vinyl alcohol) (PVA) aqueous solutions. The preshear flow was applied at 25 °C, a temperature well above the crystallization temperature. The crystalline precursors formed when the Weissenberg number (WiR=γ˙τR, defined with respect to the Rouse time) became larger than one such that polymer chains are stretched. The precursors lead to an additional relaxation process that was much slower than the chain relaxation process in the linear viscoelasticity. The precursors were very stable at 25 °C, which could be effectively smeared by application of a secondary shear flow that was much slower than the preshear, but faster than the inverse of a characteristic time scale of the slow process (arising from the crystalline precursors). During the secondary shear flow, the stress growth coefficient shows a strong stress overshoot, indicating that the flow-induced crystalline precursors had a structure akin to the associative network, probably owing to the disruption of the protective hydration shell around PVA molecules by the preshear flow, allowing the interchain hydrogen bonds to form.

Flexoelectric effect in PVDF-based copolymers and terpolymers

Compared with their inorganic counterparts, the flexoelectric effect of polymers is much less studied, and the mechanisms underlying this gradient electromechanical coupling effect have rarely been explored. In this work, the temperature dependence of the flexoelectric coefficients of PVDF-based copolymers and terpolymers was measured, and the mechanisms that affect the flexoelectric response of the polymers were investigated. For these polymers, the flexoelectric response decreases abruptly in the temperature range where the peaks of dielectric loss or mechanical loss are observed. These loss peaks originate from the phase transition or polymer chain relaxation processes. Based on this observation, we propose that the temperature dependence of the flexoelectric response of the polymers is closely related to polymer chain mobility and relaxation processes. Our study provides an in-depth understanding of the flexoelectric effect in polymers.

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.

Mechanically strong ice-templated laponite/poly(vinyl alcohol) aerogels

We report on the formation of directionally frozen ice-templated aerogels consisting of laponite and poly(vinyl alcohol). At high laponite fractions, fragile aerogels were produced while at higher polymer fraction, more rigid aerogels were produced. The freezing process led to polymer shearing and associated decrease in aerogel density via a polymer chain relaxation process after freeze-drying. The modulus of these aerogels is maximized at a laponite fraction of 0.3 due to the structure, which is comprised of columns of semi-hexagonal cells with six fold symmetry and an excess of cross-layer bridges. Such unique structure is only driven by the presence of laponite and poly(vinyl alcohol) and not by other structural driving agents (e.g. surfactant or freezing rate). Compressive modulus as high as 12MPa, with density of 0.07g/cm3 can be obtained via cryo-processing of aqueous laponite/poly(vinyl alcohol) dispersions.

Hygrothermal ageing of reprocessed polylactide

The influence of an accelerated hygrothermal ageing simulation test on a commercial PLA and its three subsequent mechanically-reprocessed materials was studied. The analysis was focused on the water diffusion kinetics and the physico-chemical changes induced by the hygrothermal degradation. Water diffusion proceeded faster than chain relaxation processes, as defined by a Case II absorption model. It was proved that the water diffusion rate decreased with subsequent reprocessing cycles and increased with higher hygrothermal ageing temperatures. Hydrolytic chain scission provoked significant molar mass decays and consequent general losses of thermal and mechanical performance. The rearrangement into crystalline fractions of shorter chains provoked by hygrothermal ageing was qualitatively and quantitatively followed by both Fourier-Transform Infrared Spectroscopy and Differential Scanning Calorimetry. The microstructural changes were monitored by the cold-crystallization temperature, the crystallinity degree XC and the absorbance intensity ratio I921/I955. A Weibull model showed that the crystallites were formed faster at higher reprocessing cycles and at lower hygrothermal ageing temperatures. All these effects were particularly significant for PLA reprocessed more than one time.

Molecular dynamics study of epoxy/clay nanocomposites: rheology and molecular confinement

To investigate the effect of nanoparticles on molecular confinement, epoxy/clay nanocomposites in 6 % wt were prepared by low shear mixer and ultrasonication methods. According to the XRD results, high energy sonication can significantly increase the intergallery space compared to that of the low shear mixer and, therefore, provide more interfacial area for polymer-particle interaction. Rheological measurements, including dynamic mechanical moduli, continuous relaxation spectrum and zero-shear viscosity, were carried out in the linear region to reveal the solid-like characteristics induced in the pure epoxy. The longest Rouse relaxation time, which was determined from the value of zero-shear viscosity, was employed to study the segmental friction. It is clear that the chain relaxation process was slowed by the polymer-particle interactions, which created very high monomeric friction. We introduce the ratio of monomeric friction coefficients (ζnano/ζepoxy) as the strength of immobilization to correlate the increasing elasticity, longer relaxation time and molecular confinement quantitatively. Because more monomers can be immobilized on a clay surface due to their strong affinity, the friction ratio increased to 359.48 for the sonicated sample, whereas weak polymer-particle affinity resulted in much lower growth, with a friction ratio of 2.11 for the low shear mixing method.

A new conduction phenomenon observed in polyethylene and epoxy resin: Ultra‐fast soliton conduction

AbstractA new conduction mechanism in polyethylene and epoxy resin is presented and discussed in this article. This mechanism is based on the presence of charge pulses that can be seen as solitons (solitary waves) crossing dielectrics with mobility 4–5 orders of magnitude larger than that of conventional charge carriers. The nature of this new process that is characterized by charge pulses with such high mobility requires a completely different mechanism for transport to be theorized with respect to that, mediated by trap sites, of conventional charge carriers. It is speculated in this article that injection and transport of positive and negative solitons occurs through the coupling of space charge and relaxation processes involving molecular chains, but of different nature for negative or positive solitons. Observation of space charge shows the existence of such solitons for at least two families of materials, polyethylene, and epoxy resin. In addition, it has been observed that nanostructuration, which is able to modify mechanical properties, affects also the presence and size of the solitons. In this article, we not only seek to demonstrate the existence of this new phenomenon, but attempt to provide an explanation and a kind of qualitative–quantitative model, which shows that the assumption of a pulsive conduction mechanism mediated by chain relaxation processes, transport in free volume (for negative solitons), and reverse‐tunneling between macromolecular chains (positive solitons) seems to fit quite well with the experimental observations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011

Fabrication and Caffeine Release from Fe3O4/P(MAA-co-NVP) Magnetic Microspheres with Controllable Core–Shell Architecture

A novel route was proposed to design and construct a magnetic composite microsphere consisting of Fe3O4 nanoparticles chemically-covalently encapsulated with pH-smart poly(methacrylic acid-co-N-vinyl pyrrolidone) (P(MAA-co-NVP)) cross-linked co-polymers by a surface-initiated radical dispersion polymerization route. The multistep surface treatment was employed to improve the dispersity and surface-chemical reactivity of Fe3O4 nanoparticles, involving introduction of active −NH2 groups, coupling of 1,1-methylene bis-(4-isocyanato-cyclohexane) and immobilization of 2,2′-azobis[2-methyl-N-(2-hydroxyethyl) propionamide]. The structure and morphological characterization was carried out by FT-IR, TEM, SEM and XRD. The chemically covalent interactions were investigated by FT-IR, TEM, TGA and DSC. The neat Fe3O4 nanoparticles took on an aggregated spherical shape with an average diameter of about 12 nm, while Fe3O4/P(MAA-co-NVP) magnetic microspheres assumed controllable and monodispersed spheres with a mean dimension of ca. 0.8 μm. The microspheres exhibited superparamagnetic properties. The in vitro caffeine release behavior under varying pH environment was investigated to evaluate the potential of Fe3O4/P(MAA-co-NVP) magnetic microspheres as a magnetic drug targeting carrier. The results indicated that the microspheres have a faster drug-release rate at pH 7.4 than at pH 1.4, corresponding to their pH swelling. The kinetic modeling demonstrated that the drug release is controlled by a balance between co-polymer chain relaxation and Fickian diffusion process, and the proposed carrier is suitable for a magnetic targeting drug-delivery system.

Understanding the effect of chain entanglement on the glass transition of a hydrophilic polymer

AbstractIn this article, we report an interesting phenomenon of the glass transition temperature (Tg) deviation of a hydrophilic polymer. Polyacrylamide (PAL) samples with different extents of chain entanglement were prepared by spray drying and solution casting. We found that the glass transition temperature increases as the extent of chain entanglement decreases upon the sub‐Tg annealing. The water content in the PAL matrix is found with no direct correlation to Tg. However, the observation of a faster diffusion process of water in the disentangled PAL matrix offers an evidence of a faster relaxation process of disentangled PAL molecules. The Tg increase of the disentangled PAL samples is believed to be associated with the increased molecular interaction during the chain relaxation process upon the sub‐Tg annealing. A macroscopic evidence is the fact that the density of the hot‐laminated samples increases as the extent of chain entanglement decreases. A thermodynamic analysis suggests that enthalpy more than entropy favors an elevated Tg of a disentangled hydrophilic polymer upon the sub‐Tg annealing. We believe that this research provides new understanding of Tg of the hydrophilic polymers, which are being extensively used in bio‐related studies. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Inhomogeneities and Chain Dynamics in Diene Rubbers Vulcanized with Different Cure Systems

In this study, we focus on qualitative differences in the network structure and dynamics of natural as well as poly(butadiene) rubber in dependence of the cure system (sulfur/accelerator or organic peroxide) used in the vulcanization process. The spatial homogeneity of the distribution of chemical and physical cross-links in the network is assessed via the quantitative measurement of proton−proton residual dipolar couplings as measured by static multiple-quantum (MQ) NMR spectroscopy at low field. The experiment also provides information on the apparent correlation time of fast segmental fluctuations that dominate chain relaxation processes at lower temperature, for which we also find characteristic differences. Vulcanization via a radical mechanism (using organic peroxides) leads to networks with a high content of nonelastic defects (loops or dangling chains), a rather inhomogeneous distribution of cross-links, and modified (slower) local dynamics, as compared to networks obtained by sulfur vulcanization. These microstructural factors can be related with the well-known differences in the macroscopic properties of diene rubbers vulcanized with different cure systems.

Dielectric Spectroscopy Investigation of Relaxation in C60−Polyisoprene Nanocomposites

We investigate the influence of adding C60 nanoparticles on the dielectric relaxation spectra of both unentangled and entangled polyisoprene (PIP). Relaxation modes corresponding to both the segmental and chain relaxation were analyzed over a broad temperature and frequency range. Regardless of whether the chains were entangled or not, both relaxation processes slowed down with the addition of C60, reflecting an increase of the nanocomposite glass transition temperature. However, C60 affects the segmental relaxation more strongly than the large-scale chain relaxation, both in terms of the relaxation time and strength, suggesting that the effect of the nanoparticles on the polymer dynamics is scale dependent. This effect is attributed to a difference in packing frustration at different length scales, a phenomenon also relevant to understanding the difference between the temperature dependence of the segmental and chain relaxation processes in neat polymer materials. Further evidence of this scale dependence is indicated by the observation that the secondary relaxation time of the high molecular mass PIP decreases with an addition of C60. These observations indicate that C60 has an effect opposite to antiplasticizing additives that slow down the secondary relaxation (stiffening the material) in the glass state, while at the same time reducing the alpha relaxation time associated with cooperative segmental and chain motions. Recent incoherent neutron scattering measurements have indicated that C60 can have a similar effect on polystyrene.

Rheological Behavior of Self-Assembling PEG-β-Cyclodextrin/PEG-Cholesterol Hydrogels

The rheological properties of a recently developed self-assembling hydrogel system composed of beta-cyclodextrin (betaCD)- and cholesterol-derivatized 8-arm star-shaped poly(ethylene glycol) (PEG8) were investigated. To understand and predict the gel rheological properties, data fitting with the Maxwell model as well as comparing the system's concentration-dependent behavior with Cates' model for reversibly breaking chains were performed. To investigate the influence of the polymer architecture, networks were also prepared by replacing the cholesterol-derivatized 8-arm star-shaped PEG by linear bifunctional PEG-cholesterol or by using 4-arm instead of 8-arm polymers. Rheological analysis showed that the 8-arm polymer-based mixtures yielded tight viscoelastic networks, but their storage and loss moduli significantly deviated from those predicted by the Maxwell model. The scaling of the plateau moduli, relaxation times, and zero-shear viscosities with concentration for gels composed of 8-arm cholesterol- and betaCD-derivatized PEG followed a power law with exponents higher than predicted by Cates' model. On the other hand, hydrogels in which linear bifunctional PEG-cholesterol was used instead of 8-arm star-shaped PEG-cholesterol or which were based on 4-arm polymers showed a substantially better fit with the Maxwell model and reduced differences between empirical and Cates' theoretical scaling exponents. Rheological analysis also showed that the hydrogels were thermoreversible. At low temperatures, the gels showed viscoelastic behavior due to slow overall relaxation of the polymer chains. At higher temperatures, however, a reduced number of betaCD/cholesterol complexes and concomitant faster chain relaxation processes eventually led to liquid-like behavior. The relationship between temperature and the relaxation time was used to determine an activation energy of 46 kJ/mol for breaking and reptation of the polymers.

Release kinetics of procaine hydrochloride (PrHy) from pH-responsive nanogels: Theory and experiments

pH-responsive nanogels consisting of methacrylic acid–ethyl acrylate (MAA–EA) cross-linked with di-allyl phthalate (DAP) were synthesized via emulsion polymerization. Drug release studies were conducted under different pHs, drug loading and concentration gradient difference. The drug loading capacity depended on the cross-link density and MAA–EA molar content, where a lower cross-link density and higher MAA–EA molar content resulted in higher loading capacity. A drug selective electrode was used to directly measure the concentration of procaine hydrochloride (PrHy) released from MAA–EA nanogels. More than 50 data points were acquired, where the mathematical fitting to the Berens and Hopfenberg model allowed the parameters describing the contributions of chain relaxation and diffusion process to be determined. The release rate increased with pH and concentration gradient difference due to a reduction in diffusion barrier and higher concentration gradient driving force, respectively, but it decreased with drug loading as the nanogel could not relax from the compact structure as evident from the contribution of Fickian diffusion, ϕ F, and chain relaxation, ϕ R. A balance between chain relaxation and Fickian diffusion process controlled the release of drugs from these pH-responsive nanogels. Exponential relationships could be established between diffusion coefficient, characteristic relaxation time and various physical parameters, where the drug release kinetics could be predicted in a quantitative manner.

Immobilization of Myoglobin from Horse Skeletal Muscle in Hydrophilic Polymer Networks.

This work examines the immobilization of myoglobin from horse skeletal muscle in hydrophilic polymer networks. Due to specific changes in the spectroscopic properties of hemoproteins during ligand binding, they could be employed in optical sensing devices. Two immobilization techniques were considered: imbibition and entrapment. Anionic hydrogels composed of methacrylic acid (MAA), cationic hydrogels composed of dimethylamino ethyl methacrylate (DMAEM), and neutral hydrogels composed of poly(ethylene glycol) monomethyl ether monomethacrylate (PEGMA; molecular weight = 200, 400, or 1000), all crosslinked with poly(ethylene glycol) dimethacrylate (PEGDMA) (molecular weight = 200, 600, or 1000), were synthesized by free-radical solution polymerization. By the imbibition method, MAA-based hydrogels incorporated the highest amount of myoglobin in comparison with PEGMA or DMAEM polymers. The evaluation of the correlation length of the networks revealed that MAA hydrogels had the highest correlation length in comparison with PEGMA-containing matrices or DMAEM hydrogels. Release experiments from MAA hydrogels at pHs 5.8 and 7.0 showed that the solute-transport mechanism was a combination of Fickian and chain relaxation diffusion. Myoglobin-loaded MAA hydrogels retained their heme reactivity after the immobilization process. The release of myoglobin incorporated by entrapment in MAA-PEGDMA hydrogels was highly influenced by the chain relaxation process. The diffusion coefficients of myoglobin incorporated by entrapment into anionic hydrogels were 2 orders of magnitude smaller (~10-13) than those for myoglobin incorporated by imbibition (10-11), both evaluated at pH 7.0. Substrate binding studies indicated that the protein biological activity was not compromised in those hydrogels loaded by the imbibition method, whereas prepolymeric solutions showed detrimental effects on protein stability.

Origin of theλTransition in Liquid Sulfur

Developing a novel experimental technique, we applied photon correlation spectroscopy using infrared radiation in liquid sulfur around T(lambda), i.e., in the temperature range where an abrupt increase in viscosity by 4 orders of magnitude is observed upon heating within few degrees. This allowed us - overcoming photoinduced and absorption effects at visible wavelengths - to reveal a chain relaxation process with characteristic time in the millisecond range. These results do rehabilitate the validity of the Maxwell relation in sulfur from an apparent failure, allowing rationalizing of the mechanical and thermodynamic behavior of this system within a viscoelastic scenario.

Factors Controlling the Rate of Photodegradation in Polymers: The Effect of Temperature on the Photodegradation Quantum Yield in a PVC Polymer Containing Metal–Metal Bonds in the Polymer Chain

The effect of temperature on the degradation quantum yield of a poly(vinyl chloride) polymer with Cp2Mo2(CO)6 units incorporated into its chains was studied (Cp = cyclopentadienyl). The polymer is photochemically reactive in the absence of oxygen because the CpMo(CO)3 radicals formed by photolysis of the Mo–Mo bonds react with C–Cl bonds to form CpMo(CO)3Cl units. Quantum yields as a function of temperature were obtained for this polymer and for two control systems, Cp′2Mo2(CO)6 dispersed in PVC and Cp′2Mo2(CO)6 in hexane/CCl4 solution (Cp′ = η5-C5H4CH3). The quantum yields of the two control systems showed only slight increases with an increase in temperature. For the reaction in hexane/CCl4, this temperature dependence is attributed to the decrease in viscosity of the solution and the subsequent decrease in the radical-radical recombination efficiency. For the Cp′2Mo2(CO)6 dispersed in PVC, the small temperature dependence is attributed to an increase in free volume as the temperature increases. In contrast to these results, the temperature dependence of the quantum yield of the PVC polymer with Cp2Mo2(CO)6 units along its chains is relatively large. It is proposed that an increase in temperature facilitates the polymer chain relaxation processes (involving recoil and rotation) following photolysis of the Mo–Mo bond. The radical–radical recombination efficiency is subsequently decreased, which leads to a net increase in chain cleavage and degradation efficiency.

Homochiral 1D Zinc−Quitenine Coordination Polymer with a High Dielectric Constant

Heat treatment of a solution of MeOH and water containing the quitenine ligand HQA [HQA = 6-methoxyl-(8S,9R)-cinchonan-9-ol-3-carboxylic acid] and ZnCl2 at 70 degrees C to give the one-dimensional (1D) chain coordination polymer {(HQA)(ZnCl2)(2.5H2O)}n (1). The local coordination geometry around the zinc center in 1 displays a slightly distorted tetrahedron, with the HQA ligand adopting a zwitterionic moiety similar to that found in natural amino acids. Measurements on a powdered sample of 1 reveal a strong second-harmonic-generation response of ca. 20 times larger than that for KDP (KH2PO4). Notably, measurements on the dielectric properties of 1 showed that the 1D chain coordination polymer exhibited a dipolar chain relaxation process and a high dielectric constant (epsilon0= 37.3).

Atomistic molecular dynamics simulation of the temperature and pressure dependences of local and terminal relaxations in cis-1,4-polybutadiene

The dynamics of cis-1,4-polybutadiene (cis-1,4-PB) over a wide range of temperature and pressure conditions is explored by conducting atomistic molecular dynamics (MD) simulations with a united atom model on a 32-chain C128 cis-1,4-PB system. The local or segmental dynamics is analyzed in terms of the dipole moment time autocorrelation function (DACF) of the simulated polymer and its temperature and pressure variations, for temperatures as low as 195 K and pressures as high as 3 kbars. By Fourier transforming the DACF, the dielectric spectrum, epsilon* = epsilon' + i epsilon" = epsilon*omega, is computed and the normalized epsilon"/epsilon(max)" vs omega/omega(max) plot is analyzed on the basis of the time-temperature and time-pressure superposition principles. The relative contribution of thermal energy and volume to the segmental and chain relaxation processes are also calculated and evaluated in terms of the ratio of the activation energy at constant volume to the activation energy at constant pressure, Q(V)/Q(P). Additional results for the temperature and pressure dependences of the Rouse times describing terminal relaxation in the two polymers show that, in the regime of the temperature and pressure conditions covered here, segmental and chain relaxations are influenced similarly by the pressure and temperature variations. This is in contrast to what is measured experimentally [see, e.g., G. Floudas and T. Reisinger, J. Chem. Phys. 111, 5201 (1999); C. M. Roland et al.,J. Polym. Sci. Part B, 41, 3047 (2003)] for other, chemically more complex polymers that pressure has a stronger influence on the dynamics of segmental mode than on the dynamics of the longest normal mode, at least for the regime of temperature and pressure conditions covered in the present MD simulations.