Biomedical subjects

D Leporini

Publications and source records attributed to D Leporini.

14 recordsLinked to original sources

PubMed2005

Signatures of the fast dynamics in glassy polystyrene: first evidence by high-field electron paramagnetic resonance of molecular guests.

The reorientation of one small paramagnetic molecule (spin probe) in glassy polystyrene (PS) is studied by high-field electron paramagnetic resonance spectroscopy at two different Larmor frequencies (190 and 285 GHz). Two different regimes separated by a crossover region are evidenced. Below 180 K the rotational times are nearly temperature independent with no apparent distribution. In the temperature range of 180-220 K a large increase of the rotational mobility is observed with the widening of the distribution of correlation times which exhibits two components: (i) a deltalike, temperature-independent component representing the fraction of spin probes w which persist in the low-temperature dynamics; (ii) a strongly temperature-dependent component, to be described by a power distribution, representing the fraction of spin probes 1-w undergoing activated motion over an exponential distribution of barrier heights g(E). Above 180 K a steep decrease of w is evidenced. The shape and the width of g(E) do not differ from the reported ones for PS within the errors. For the first time the large increase of the rotational mobility of the spin probe at 180 K is ascribed to the onset of the fast dynamics detected by neutron scattering at T(f)=175+/-25 K.

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PubMed2005

A manifestation of the Ostwald step rule: molecular-dynamics simulations and free-energy landscape of the primary nucleation and melting of single-molecule polyethylene in dilute solution.

The paper presents numerical results from extensive molecular-dynamics simulations of the crystallization process of a single polyethylene chain with N=500 monomers. The development of the ordered structure is seen to proceed along different routes involving either the global reorganization of the chain or, alternatively, well-separated connected nuclei. No dependence on the thermal history was observed at the late stages of the crystallization. The folding process involves several intermediate ordered metastable states, in strong analogy with the experiments, and ends up in a well-defined long-lived lamella with ten stems of approximately equal length, arranged into a regular, hexagonal pattern. This behavior may be seen as a microscopic manifestation of the Ostwald step rule. Both the metastable states and the long-lived one are evidenced as the local minima and the global one of the free-energy landscape, respectively. The study of the microscopic organization of the lamella evidenced that the two caps are rather flat, i.e., the loops connecting the stems are short. Interestingly, annealing the chain through the different metastable states leaves the average number of monomers per loop nearly unchanged. It is also seen that the chain ends, the so-called cilia, are localized on the surface of the lamella, in agreement with the experiments, and that structural fluctuations take place on the lamella surface, as noted by recent Monte Carlo simulations. The study of the melting process evidences that the degree of hysteresis is small.

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PubMed2004

Role of the density in the crossover region of o-terphenyl and poly(vinyl acetate).

The coupling between the reorientation of molecular probes and the density in one low-molar mass glass former [ o -terphenyl (OTP)] and one polymer [poly(vinyl acetate) (PVAc)] is studied in the Goldstein's crossover region where the structural (alpha) and the secondary (beta) relaxations bifurcate. The coupling is found to be strong in OTP and virtually absent in PVAc. The probes sense both the alpha and beta relaxations, and locate their splitting accurately. It is concluded that the density affects the relaxation occurring in the crossover region of OTP but not of PVAc at subnanometer length scales. The findings are compared with recent assessments of the role of the molecular packing close and above the glass transition temperature T(g).

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PubMed2004

Molecular dynamics study of the thermal and the density effects on the local and the large-scale motion of polymer melts: scaling properties and dielectric relaxation.

Results from a molecular dynamics simulation of a melt of unentangled polymers are presented. The translational motion, the large-scale and the local reorientation processes of the chains, as well as their relations with the so-called "normal" and "segmental" dielectric relaxation modes are thoroughly investigated in wide temperature and pressure ranges. The thermodynamic states are well fitted by the phenomenological Tait equation of state. A global time-temperature-pressure superposition principle of both the translational and the rotational dynamics is evidenced. The scaling is more robust than the usual Rouse model. The latter provides insight but accurate comparison with the simulation calls for modifications to account for both the local chain stiffness and the nonexponential relaxation. The study addresses the issue whether the temperature or the density is a dominant control parameter of the dynamics or the two quantities give rise to comparable effects. By examining the ratio /alphatau//alphaP between the isochronic and isobaric expansivities, one finds that the temperature is dominant when the dynamics is fast. If the relaxation slows down, the fluctuations of the free volume increase their role and become comparable to those of the thermal energy. Detectable cross-correlation between the "normal-mode" and the "segmental" dielectric relaxations is found and contrasted with the usual assumption of independent modes.

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PubMed2001

Viscous flow and jump dynamics in molecular supercooled liquids. I. Translations.

The transport and relaxation properties of a molecular supercooled liquid on an isobar are studied by molecular dynamics. The molecule is a rigid heteronuclear biatomic system. The diffusivity is fitted over four orders of magnitude by the power law D proportional to (T-T(c))(gamma(D)), with gamma(D)=1.93+/-0.02 and T(c)=0.458+/-0.002. The self-part of the intermediate scattering function F(s)(k(max),t) exhibits a steplike behavior at the lowest temperatures. On cooling, the increase of the related relaxation time tau(alpha) tracks the diffusivity, i.e., tau(alpha) proportional to (k(2)(max)D)(-1). At the lowest temperatures, fractions of highly mobile and trapped molecules are also evidenced. Translational jumps are also evidenced. The duration of the jumps exhibits a distribution. The distribution of the waiting times before a jump takes place, psi(t), is exponential at higher temperatures. At lower temperatures a power-law divergence is evidenced at short times, psi(t) proportional to t(xi-1) with 0<xi<or=1, which is ascribed to intermittency. The shear viscosity is fitted by the power law eta proportional to (T-T(c))(gamma(eta)), with gamma(eta)=-2.20+/-0.03 at the lowest temperatures. At higher temperatures the Stokes-Einstein relation fits the data if stick boundary conditions are assumed. The product D eta/T increases at lower temperatures, and the Stokes-Einstein relation breaks down at a temperature which is close to the one where the intermittency is evidenced by psi(t). A precursor effect of the breakdown is observed, which manifests itself as an apparent stick-slip transition.

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PubMed2001

Viscous flow and jump dynamics in molecular supercooled liquids. II. Rotations.

The rotational dynamics of a supercooled model liquid of rigid A-B dumbbells interacting via a Lennard-Jones potential is investigated along one single isobar. The time-temperature superposition principle, one key prediction of mode-coupling theory (MCT), was studied for the orientational correlation functions C(l). In agreement with previous studies we found that the scaling of C(l) in a narrow region at long times is better at high-l values. However, on a wider time interval the scaling works fairly better at low-l values. Consistently, we observed the remarkable temperature dependence of the rotational correlation time tau(1) as a power law in T-T(c) over more than three orders of magnitude and the increasing deviations from that law on increasing l (T(c) is the MCT critical temperature). For 0.7<T<2, good agreement with the diffusion model is found. For lower temperatures the agreement becomes poorer, and the results are also only partially accounted for by the jump-rotation model. The angular Van Hove function shows that in this region a meaningful fraction of the sample reorientates by jumps of about 180 degrees. The distribution of the waiting times in the angular sites cuts exponentially at long times. At lower temperatures it decays at short times as t(xi-1), with xi=0.34+/-0.04 at T=0.5, in analogy with the translational case. The breakdown of the Debye-Stokes-Einstein relation is observed at lower temperatures, where the rotational correlation times diverge more weakly than the viscosity.

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PubMed1998

Measurement of the longitudinal relaxation time by continuous-wave, nonlinear electron spin resonance spectroscopies

We characterize a continuous-wave, nonlinear electron spin resonance spectroscopy which detects the longitudinal component of the magnetization. It is demonstrated that the signal is proportional to the Laplace transform of a relaxation function with decay time equal to the longitudinal relaxation time T1. The conclusion is reached by comparing T1 to the effective time T(eff)1 being drawn by progressive saturation for a nitroxide radical dissolved in supercooled o-terphenyl. Copyright 1998 Academic Press.

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PubMed1995