468 research outputs found
On the Molecular Origin of the Cooperative Coil-to-globule Transition of Poly(N-isopropylacrylamide) in Water
By means of atomistic molecular dynamics simulations we investigate the
behaviour of poly(N-isopropylacrylamide), PNIPAM, in water at temperatures
below and above the lower critical solution temperature (LCST), including the
undercooled regime. The transition between water soluble and insoluble states
at the LCST is described as a cooperative process involving an intramolecular
coil-to-globule transition preceding the aggregation of chains and the polymer
precipitation. In this work we investigate the molecular origin of such
cooperativity and the evolution of the hydration pattern in the undercooled
polymer solution. The solution behaviour of an atactic 30-mer at high dilution
is studied in the temperature interval from 243 to 323 K with a favourable
comparison to available experimental data. In the PNIPAM water soluble states
we detect a correlation between polymer segmental dynamics and diffusion motion
of bound water, occurring with the same activation energy. Simulation results
show that below the coil-to-globule transition temperature PNIPAM is surrounded
by a network of hydrogen bonded water molecules and that the cooperativity
arises from the structuring of water clusters in proximity to hydrophobic
groups. Differently, the perturbation of the hydrogen bond pattern involving
water and amide groups occurs above the transition temperature. Altogether
these findings reveal that even above the LCST PNIPAM remains largely hydrated
and that the coil-to-globule transition is related with a significant
rearrangement of the solvent in proximity of the surface of the polymer. The
comparison between the hydrogen bonding of water in the surrounding of PNIPAM
isopropyl groups and in bulk displays a decreased structuring of solvent at the
hydrophobic polymer-water interface across the transition temperature, as
expected because of the topological extension along the chain of such
interface
Numerical modelling of non-ionic microgels: an overview
Microgels are complex macromolecules. These colloid-sized polymer networks
possess internal degrees of freedom and, depending on the polymer(s) they are
made of, can acquire a responsiveness to variations of the environment
(temperature, pH, salt concentration, etc.). Besides being valuable for many
practical applications, microgels are also extremely important to tackle
fundamental physics problems. As a result, these last years have seen a rapid
development of protocols for the synthesis of microgels, and more and more
research has been devoted to the investigation of their bulk properties.
However, from a numerical standpoint the picture is more fragmented, as the
inherently multi-scale nature of microgels, whose bulk behaviour crucially
depends on the microscopic details, cannot be handled at a single level of
coarse-graining. Here we present an overview of the methods and models that
have been proposed to describe non-ionic microgels at different length-scales,
from the atomistic to the single-particle level. We especially focus on
monomer-resolved models, as these have the right level of details to capture
the most important properties of microgels, responsiveness and softness. We
suggest that these microscopic descriptions, if realistic enough, can be
employed as starting points to develop the more coarse-grained representations
required to investigate the behaviour of bulk suspensions
Numerical study of the glass-glass transition in short-ranged attractive colloids
We report extensive numerical simulations in the {\it glass} region for a
simple model of short-ranged attractive colloids, the square well model. We
investigate the behavior of the density autocorrelation function and of the
static structure factor in the region of temperatures and packing fractions
where a glass-glass transition is expected according to theoretical
predictions. We strengthen our observations by studying both waiting time and
history dependence of the numerical results. We provide evidence supporting the
possibility that activated bond-breaking processes destabilize the attractive
glass, preventing the full observation of a sharp glass-glass kinetic
transition.Comment: 15 pages, 9 figures; Proceedings of "Structural Arrest Transitions in
Colloidal Systems with Short-Range Attractions", Messina, Italy, December
2003 (submitted to J. Phys.: Condens. Matt.
Structural Relaxation of a Gel Modeled by Three Body Interactions
We report a molecular dynamics simulation study of a model gel whose
interaction potential is obtained by modifying the three body Stillinger-Weber
model potential for silicon. The modification reduces the average coordination
number, and suppresses the liquid-gas phase coexistence curve. The low density,
low temperature equilibrium gel that can thus form exhibits interesting
dynamical behavior, including compressed exponential relaxation of density
correlations. We show that motion responsible for such relaxation has ballistic
character, and arises from the motion of chain segments in the gel without the
restructuring of the gel network.Comment: 5 pages, 5 figure
A shear wave analysis system for semi-automatic measurements of shear wave splitting above volcanic earthquakes: descriptions and applications
Our interest is the study of the seismograms with the purpose of monitoring and modelling
volcanoes. In particular, since the shear waves bring information about the anisotropic system
characterizing the shallow crust, they are also sensitive to all temporal variations caused by
changes in the stress field acting on the area. Therefore we intend to realize an algorithm that
can provide shear wave splitting estimates in quasi-real time and in a semi-automatic way.
Finally we perform validation tests on both real and synthetic data, in order to define the
accuracy and validity range of our program
Molecular insights on poly(N-isopropylacrylamide) coil-to-globule transition induced by pressure
By using extensive all-atom molecular dynamics simulations of an atactic linear polymer chain, we provide microscopic insights into poly(N-isopropylacrylamide) (PNIPAM) coil-to-globule transition addressing the roles played by both temperature and pressure. We detect a coil-to-globule transition up to large pressures, showing a reentrant behavior of the critical temperature with increasing pressure in agreement with experimental observations. Furthermore, again confirming the experimental findings, we report the existence at high pressures of a new kind of globular state. It is characterized by a more structured hydration shell that is closer to PNIPAM hydrophobic domains, as compared to the globular state observed at atmospheric pressure. Our results highlight that temperature and pressure induce a PNIPAM coil-to-globule transition through different molecular mechanisms, opening the way for a systematic use of both thermodynamic variables to tune the location of the transition and the properties of the associated swollen/collapsed states
Gelation as arrested phase separation in short-ranged attractive colloid-polymer mixtures
We present further evidence that gelation is an arrested phase separation in
attractive colloid-polymer mixtures, based on a method combining confocal
microscopy experiments with numerical simulations recently established in {\bf
Nature 453, 499 (2008)}. Our results are independent of the form of the
interparticle attractive potential, and therefore should apply broadly to any
attractive particle system with short-ranged, isotropic attractions. We also
give additional characterization of the gel states in terms of their structure,
inhomogeneous character and local density.Comment: 6 figures, to be published in J. Phys. Condens. Matter, special issue
for EPS Liquids Conference 200
Harmonic damped oscillators with feedback. A Langevin study
We consider a system in direct contact with a thermal reservoir and which, if
left unperturbed, is well described by a memory-less equilibrium Langevin
equation of the second order in the time coordinate. In such conditions, the
strength of the noise fluctuations is set by the damping factor, in accordance
with the Fluctuation and Dissipation theorem. We study the system when it is
subject to a feedback mechanism, by modifying the Langevin equation
accordingly. Memory terms now arise in the time evolution, which we study in a
non-equilibrium steady state. Two types of feedback schemes are considered, one
focusing on time shifts and one on phase shifts, and for both cases we evaluate
the power spectrum of the system's fluctuations. Our analysis finds application
in feedback cooled oscillators, such as the Gravitational Wave detector AURIGA.Comment: 17 page
Competing interactions in arrested states of colloidal clays
Using experiments, theory and simulations, we show that the arrested state
observed in a colloidal clay at intermediate concentrations is stabilized by
the screened Coulomb repulsion (Wigner glass). Dilution experiments allow us to
distinguish this high-concentration disconnected state, which melts upon
addition of water, from a low-concentration gel state, which does not melt.
Theoretical modelling and simulations reproduce the measured Small Angle X-Ray
Scattering static structure factors and confirm the long-range electrostatic
nature of the arrested structure. These findings are attributed to the
different timescales controlling the competing attractive and repulsive
interactions.Comment: Accepted for publication in Physical Review Letter
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