88 research outputs found
The many origins of charge inversion in electrolyte solutions: effects of discrete interfacial charges
We show that charge inversion, i.e. interfacial charges attracting
counterions in excess of their own nominal charge, is a general effect that
takes place in most charged systems next to aqueous solutions with multivalent
ions and identify three different electrostatic origins for this effect 1)
counterion-counterion correlations, 2) correlations between counterions and
interfacial charges and 3) complexation. We briefly describe the first two
regimes and provide a detailed characterization of the complexation regime from
united atom molecular dynamics simulation of a phospholipid domain in contact
with an aqueous solution. We examine the expected conditions where each regime
should apply and describe a representative experimental example to illustrate
each case. We point out that our results provide a characterization of ionic
distributions irrespectively of whether charge inversion takes place and show
that processes such as proton release and transfer are also linked to ionic
correlations. We conclude with a discussion of further experimental and
theoretical implications.Comment: 22 pages, 7 figure
Charge Inversion of Divalent Ionic Solutions in Silica Channels
Recent experiments (F.H.J. Van Der Heyden et al., PRL 96, 224502 (2006)) of
streaming currents in silica nanochannels with divalent ions report charge
inversion, i.e. interfacial charges attracting counterions in excess of their
own nominal charge, in conflict with existing theoretical and simulation
results. We reveal the mechanism of charge inversion by using all-atomic
molecular dynamics simulations. Our results show excellent agreement with
experiments, both qualitatively and quantitatively. We further discuss the
implications of our study for the general problem of ionic correlations in
solutions as well as in regards of the properties of silica-water interfaces.Comment: 5 pages, 5 figure
Origin of the short-range, strong repulsive force between ionic surfactant layers
We study the electrostatic interaction between two ionic surfactant layers by performing molecular dynamic simulations of salt-free thin water films coated by surfactants (Newton black films). We find a strong exponentially decaying short-range repulsion not explained by classical Poisson-Boltzmann theory. This electrostatic force is shown to be mainly due to the anomalous dielectric response of water near charged surfactant layers. This result clarifies the much debated physical mechanism underlying the controversial "hydration forces" observed in experiments. In the case of ionic thin films, the "hydration forces" can be identified with the electrostatic forces induced by the layers of highly polarized water originated at the interfaces
Evaluation of a New, Rapid, Fully Automated Assay for the Measurement of ADAMTS13 Activity
Thrombotic thrombocytopenic purpura (TTP) is a rare thrombotic microangiopathy (TMA) characterized by the severe deficiency of a disintegrin and metalloproteinase with a thrombospondin type 1 motif, member 13 (ADAMTS13) activity (< 10%). Rapid ADAMTS13 testing is crucial for an early diagnosis and optimal management of acute TTP. We evaluated the performance of the HemosIL AcuStar ADAMTS13 activity assay (Instrumentation Laboratory, Bedford, Massachusetts, United States), a fully automated chemiluminescent immunoassay with an analytical time of 33 minutes. A method comparison study was performed on 176 samples from 49 healthy donors and 127 TMA patients (109 TTP, 7 atypical hemolytic uremic syndrome, 11 other TMAs), comparing this new assay with an in-house FRETS-VWF73 assay and a commercial enzyme-linked immunosorbent assay (ELISA) (TECHNOZYM ADAMTS-13 Activity, Technoclone GmbH, Vienna, Austria). Agreement between methods was assessed with focus on ADAMTS13 activity less than 10%, the medical decision level relevant for TTP diagnosis. The HemosIL AcuStar ADAMTS13 Activity showed good correlation with both the FRETS-VWF73 (r = 0.96) and ELISA (r = 0.96) methods. Slope of the Passing-Bablok regression was 1.05 for FRETS-VWF73 and 1.02 for ELISA, and absolute bias at the medical decision level was +0.1 and +0.3%, respectively. The study also revealed high agreement with FRETS-VWF73 (kappa 0.97) and ELISA (kappa 0.98) methods in classifying TTP patients with a severe deficiency of ADAMTS13 activity. Because of its short turnaround time and full automation, the HemosIL AcuStar ADAMTS13 activity assay might become the assay of choice to rapidly test ADAMTS13 activity in plasma and thus establish the diagnosis of acute TTP in emergency settings
Curvature-coupling dependence of membrane protein diffusion coefficients
We consider the lateral diffusion of a protein interacting with the curvature
of the membrane. The interaction energy is minimized if the particle is at a
membrane position with a certain curvature that agrees with the spontaneous
curvature of the particle. We employ stochastic simulations that take into
account both the thermal fluctuations of the membrane and the diffusive
behavior of the particle. In this study we neglect the influence of the
particle on the membrane dynamics, thus the membrane dynamics agrees with that
of a freely fluctuating membrane. Overall, we find that this curvature-coupling
substantially enhances the diffusion coefficient. We compare the ratio of the
projected or measured diffusion coefficient and the free intramembrane
diffusion coefficient, which is a parameter of the simulations, with analytical
results that rely on several approximations. We find that the simulations
always lead to a somewhat smaller diffusion coefficient than our analytical
approach. A detailed study of the correlations of the forces acting on the
particle indicates that the diffusing inclusion tries to follow favorable
positions on the membrane, such that forces along the trajectory are on average
smaller than they would be for random particle positions.Comment: 16 pages, 8 figure
Superparamagnetic colloids in viscous fluids
The influence of a magnetic field on the aggregation process of superparamagnetic colloids has been well known on short time for a few decades. However, the influence of important parameters, such as viscosity of the liquid, has received only little attention. Moreover, the equilibrium state reached after a long time is still challenging on some aspects. Indeed, recent experimental measurements show deviations from pure analytical models in extreme conditions. Furthermore, current simulations would require several years of computing time to reach equilibrium state under those conditions. In the present paper, we show how viscosity influences the characteristic time of the aggregation process, with experimental measurements in agreement with previous theories on transient behaviour. Afterwards, we performed numerical simulations on equivalent systems with lower viscosities. Below a critical value of viscosity, a transition to a new aggregation regime is observed and analysed. We noticed this result can be used to reduce the numerical simulation time from several orders of magnitude, without modifying the intrinsic physical behaviour of the particles. However, it also implies that, for high magnetic fields, granular gases could have a very different behaviour from colloidal liquids
Variational Methods for Biomolecular Modeling
Structure, function and dynamics of many biomolecular systems can be
characterized by the energetic variational principle and the corresponding
systems of partial differential equations (PDEs). This principle allows us to
focus on the identification of essential energetic components, the optimal
parametrization of energies, and the efficient computational implementation of
energy variation or minimization. Given the fact that complex biomolecular
systems are structurally non-uniform and their interactions occur through
contact interfaces, their free energies are associated with various interfaces
as well, such as solute-solvent interface, molecular binding interface, lipid
domain interface, and membrane surfaces. This fact motivates the inclusion of
interface geometry, particular its curvatures, to the parametrization of free
energies. Applications of such interface geometry based energetic variational
principles are illustrated through three concrete topics: the multiscale
modeling of biomolecular electrostatics and solvation that includes the
curvature energy of the molecular surface, the formation of microdomains on
lipid membrane due to the geometric and molecular mechanics at the lipid
interface, and the mean curvature driven protein localization on membrane
surfaces. By further implicitly representing the interface using a phase field
function over the entire domain, one can simulate the dynamics of the interface
and the corresponding energy variation by evolving the phase field function,
achieving significant reduction of the number of degrees of freedom and
computational complexity. Strategies for improving the efficiency of
computational implementations and for extending applications to coarse-graining
or multiscale molecular simulations are outlined.Comment: 36 page
Horizontal low gradient magnetophoresis behaviour of iron oxide nanoclusters at the different steps of the synthesis route
In this work the use of Horizontal Low Gradient Magnetic Field (HLGMF) (<100T/m) for filtration, control and separation of synthesized magnetic nanoparticles (NPs) is investigated. The characteristics of the suspension, size and type of the NPs are considered and discussed. For these purposes, Fe2O3 silica coated nanoclusters of about 150 nm are synthesized by co-precipitation, monodispersion and silica coating. SQUID, TEM, XRD, and z potential techniques were used to characterize the synthesized nanoclusters. An extensive magnetophoresis study was performed at different magnetophoretical conditions. Different reversible aggregation times were observed at different HLGMF, at each step of the synthesis route. In particular, differences of several orders of magnitude were observed when comparing citric acid modified NPs with silica coated nanoclusters . Reversible aggregation times are correlated to the properties of the NPs at different steps of synthesis route.Fundação para a Ciência e a Tecnologia (FCT) - Bolsa NANO/NMed-SD/0156/2007, PTCD/CTM/69316/2006
Calcium Triggered Lα-H2 Phase Transition Monitored by Combined Rapid Mixing and Time-Resolved Synchrotron SAXS
BACKGROUND: Awad et al. reported on the Ca(2+)-induced transitions of dioleoyl-phosphatidylglycerol (DOPG)/monoolein (MO) vesicles to bicontinuous cubic phases at equilibrium conditions. In the present study, the combination of rapid mixing and time-resolved synchrotron small-angle X-ray scattering (SAXS) was applied for the in-situ investigations of fast structural transitions of diluted DOPG/MO vesicles into well-ordered nanostructures by the addition of low concentrated Ca(2+) solutions. METHODOLOGY/PRINCIPAL FINDINGS: Under static conditions and the in absence of the divalent cations, the DOPG/MO system forms large vesicles composed of weakly correlated bilayers with a d-spacing of approximately 140 A (L(alpha)-phase). The utilization of a stopped-flow apparatus allowed mixing these DOPG/MO vesicles with a solution of Ca(2+) ions within 10 milliseconds (ms). In such a way the dynamics of negatively charged PG to divalent cation interactions, and the kinetics of the induced structural transitions were studied. Ca(2+) ions have a very strong impact on the lipidic nanostructures. Intriguingly, already at low salt concentrations (DOPG/Ca(2+)>2), Ca(2+) ions trigger the transformation from bilayers to monolayer nanotubes (inverted hexagonal phase, H(2)). Our results reveal that a binding ratio of 1 Ca(2+) per 8 DOPG is sufficient for the formation of the H(2) phase. At 50 degrees C a direct transition from the vesicles to the H(2) phase was observed, whereas at ambient temperature (20 degrees C) a short lived intermediate phase (possibly the cubic Pn3m phase) coexisting with the H(2) phase was detected. CONCLUSIONS/SIGNIFICANCE: The strong binding of the divalent cations to the negatively charged DOPG molecules enhances the negative spontaneous curvature of the monolayers and causes a rapid collapsing of the vesicles. The rapid loss of the bilayer stability and the reorganization of the lipid molecules within ms support the argument that the transition mechanism is based on a leaky fusion of the vesicles
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