376 research outputs found
The Osmotic Coefficient of Rod-like Polyelectrolytes: Computer Simulation, Analytical Theory, and Experiment
The osmotic coefficient of solutions of rod-like polyelectrolytes is
considered by comparing current theoretical treatments and simulations to
recent experimental data. The discussion is restricted to the case of
monovalent counterions and dilute, salt-free solutions. The classical
Poisson-Boltzmann solution of the cell model correctly predicts a strong
decrease in the osmotic coefficient, but upon closer look systematically
overestimates its value. The contribution of ion-ion-correlations are
quantitatively studied by MD simulations and the recently proposed DHHC theory.
However, our comparison with experimental data obtained on synthetic,
stiff-chain polyelectrolytes shows that correlation effects can only partly
explain the discrepancy. A quantitative understanding thus requires theoretical
efforts beyond the restricted primitive model of electrolytes.Comment: 16 pages, 2 figure
Structure factor and thermodynamics of rigid dendrimers in solution
The ''polymer reference interaction site model'' (PRISM) integral equation
theory is used to determine the structure factor of rigid dendrimers in
solution. The theory is quite successful in reproducing experimental structure
factors for various dendrimer concentrations. In addition, the structure factor
at vanishing scattering vector is calculated via the compressibility equation
using scaled particle theory and fundamental measure theory. The results as
predicted by both theories are systematically smaller than the experimental and
PRISM data for platelike dendrimers.Comment: 7 pages, 5 figures, submitte
Adsorption of Mono- and Divalent Ions onto Dendritic Polyglycerol Sulfate (dPGS) as Studied Using Isothermal Titration Calorimetry
The effective charge of highly charged polyelectrolytes is significantly lowered by a condensation of counterions. This effect is more pronounced for divalent ions. Here we present a study of the counterion condensation to dendritic polyglycerol sulfate (dPGS) that consists of a hydrophilic dendritic scaffold onto which sulfate groups are appended. The interactions between the dPGS and divalent ions (Mg2+ and Ca2+) were analyzed using isothermal titration calorimetry (ITC) and showed no ion specificity upon binding, but clear competition between the monovalent and divalent ions. Our findings, in line with the latest theoretical studies, demonstrate that a large fraction of the monovalent ions is sequentially replaced with the divalent ions
Competitive adsorption of multiple proteins to nanoparticles: the Vroman effect revisited
Proteins adsorbed from the blood plasma change nanoparticles inter- actions with the surrounding biological environment. In general, the ad- sorption of multiple proteins has a non-monotonic time dependence, that is, proteins adsorbed at first may slowly be replaced by others. This “Vro- man effect” leads to a highly dynamic protein corona on nanoparticles that profoundly influences the immune response of the body. Thus, the temporal evolution of the corona must be taken into account when consid- ering applications of nanocarriers in, e.g., nanomedicine or drug delivery. Up to now, the Vroman effect is explained solely in terms of diffusion: Smaller proteins which diffuse faster are adsorbed first while larger ones, having a stronger interaction with the surface, are preferred at equilib- rium. Here we use dynamic density functional theory (DDFT) including steric and electrostatic interactions to provide a full model for the tem- poral evolution of the protein corona. In particular, we demonstrate that proper consideration of all interactions leads to Vroman-like adsorption signatures in widely different scenarios. Moreover, consideration of ener- getic terms predicts both competitive as well as co-operative adsorption. In this way, DDFT provides a reacher picture of the evolution of the dynamic protein coron
Interaction of Charged Patchy Protein Models with Like Charged Polyelectrolyte Brushes
We study the adsorption of charged patchy particle models (CPPMs) on a thin
film of a like-charged and dense polyelectrolyte (PE) brush (of 50 monomers per
chain) by means of implicit-solvent, explicit-salt Langevin dynamics computer
simulations. Our previously introduced set of CPPMs embraces well-defined one-,
and two-patched spherical globules, each of the same net charge and (nanometer)
size, with mono- and multipole moments comparable to those of small globular
proteins. We focus on electrostatic effects on the adsorption far away from the
isoelectric point of typical proteins, i.e., where charge regulation plays no
role. Despite the same net charge of the brush and globule we observe large
binding affinities up to tens of the thermal energy, kT, which are enhanced by
decreasing salt concentration and increasing charge of the patch(es). Our
analysis of the distance-resolved potentials of mean force together with a
phenomenological description of all leading interaction contributions shows
that the attraction is strongest at the brush surface, driven by multipolar,
Born (self-energy), and counterion-release contributions, dominating locally
over the monopolar and steric repulsions.Comment: 16 pages, 8 figures, 2 table
Quantifying the Reversible Association of Thermosensitive Nanoparticles
Under many conditions, biomolecules and nanoparticles associate by means of
attractive bonds, due to hydrophobic attraction. Extracting the microscopic
association or dissociation rates from experimental data is complicated by the
dissociation events and by the sensitivity of the binding force to temperature
(T). Here we introduce a theoretical model that combined with light-scattering
experiments allows us to quantify these rates and the reversible binding energy
as a function of T. We apply this method to the reversible aggregation of
thermoresponsive polystyrene/poly(N-isopropylacrylamide) core-shell
nanoparticles, as a model system for biomolecules. We find that the binding
energy changes sharply with T, and relate this remarkable switchable behavior
to the hydrophobic-hydrophilic transition of the thermosensitive nanoparticles
Residual Stresses in Glasses
The history dependence of the glasses formed from flow-melted steady states
by a sudden cessation of the shear rate is studied in colloidal
suspensions, by molecular dynamics simulations, and mode-coupling theory. In an
ideal glass, stresses relax only partially, leaving behind a finite persistent
residual stress. For intermediate times, relaxation curves scale as a function
of , even though no flow is present. The macroscopic stress
evolution is connected to a length scale of residual liquefaction displayed by
microscopic mean-squared displacements. The theory describes this history
dependence of glasses sharing the same thermodynamic state variables, but
differing static properties.Comment: submitted to Physical Revie
Catalysis by metallic nanoparticles in solution: thermosensitive microgels as nanoreactors
Metallic nanoparticles have been used as catalysts for various reactions, and the huge literature on the subject is hard to overlook. In many applications, the nanoparticles must be affixed to a colloidal carrier for easy handling during catalysis. These "passive carriers" (e.g. dendrimers) serve for a controlled synthesis of the nanoparticles and prevent coagulation during catalysis. Recently, hybrids from nanoparticles and polymers have been developed that allow us to change the catalytic activity of the nanoparticles by external triggers. In particular, single nanoparticles embedded in a thermosensitive network made from poly(N-isopropylacrylamide) (PNIPAM) have become the most-studied examples of such hybrids: immersed in cold water, the PNIPAM network is hydrophilic and fully swollen. In this state, hydrophilic substrates can diffuse easily through the network, and react at the surface of the nanoparticles. Above the volume transition located at 32°C, the network becomes hydrophobic and shrinks. Now hydrophobic substrates will preferably diffuse through the network and react with other substrates in the reaction catalyzed by the enclosed nanoparticle. Such "active carriers", may thus be viewed as true nanoreactors that open new ways for the use of nanoparticles in catalysis. In this review, we give a survey on recent work done on these hybrids and their application in catalysis. The aim of this review is threefold: we first review hybrid systems composed of nanoparticles and thermosensitive networks and compare these "active carriers" to other colloidal and polymeric carriers (e.g. dendrimers). In a second step we discuss the model reactions used to obtain precise kinetic data on the catalytic activity of nanoparticles in various carriers and environments. These kinetic data allow us to present a fully quantitative comparison of different nanoreactors. In a final section we shall present the salient points of recent efforts in the theoretical modeling of these nanoreactors. By accounting for the presence of a free-energy landscape for the reactants' diffusive approach towards the catalytic nanoparticle, arising from solvent-reactant and polymeric shell-reactant interactions, these models are capable of explaining the emergence of all the important features observed so far in studies of nanoreactors. The present survey also suggests that such models may be used for the design of future carrier systems adapted to a given reaction and solvent
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