arXiv subjects

Matthias Ballauff

Publications and source records attributed to Matthias Ballauff.

At least 19 recordsLinked to original sources

arXiv2020

Charge and hydration structure of dendritic polyelectrolytes: molecular simulations of polyglycerol sulphate

Macromolecules based on dendritic or hyperbranched polyelectrolytes have been emerging as high potential candidates for biomedical applications. Here we study the charge and solvation structure of dendritic polyglycerol sulphate (dPGS) of generations 0 to 3 in aqueous sodium chloride solution by explicit-solvent molecular dynamics computer simulations. We characterize dPGS by calculating several important properties such as relevant dPGS radii, molecular distributions, the solvent accessible surface area, and the partial molecular volume. In particular, as the dPGS exhibits high charge renormalization effects, we address the challenges of how to obtain a well-defined effective charge and surface potential of dPGS for practical applications. We compare implicit- and explicit-solvent approaches in our all-atom simulations with the coarse-grained simulations from our previous work. We find consistent values for the effective electrostatic size (i.e., the location of the effective charge of a Debye--Hückel sphere) within all the approaches, deviating at most by the size of a water molecule. Finally, the excess chemical potential of water insertion into dPGS and its thermodynamic signature are presented and rationalized.

cond-mat.soft↗

arXiv2020

Structural and Transport Properties of Li/S Battery Electrolytes: Role of the Polysulfide Species

Lithium--sulfur (Li/S) batteries are regarded as one of the most promising energy storage devices beyond lithium-ion batteries because of their high energy density of 2600 Wh/kg and an affordable cost of sulfur. Meanwhile, some challenges inherent to Li/S batteries remain to be tackled, for instance, the polysulfide (PS) shuttle effect, the irreversible solidification of Li$_2$S, and the volume expansion of the cathode material during discharge. On the molecular level, these issues originate from the structural and solubility behavior of the PS species in bulk and in the electrode confinement. In this study, we use classical molecular dynamics (MD) simulations to develop a working model for PS of different chain lengths in applied electrolyte solutions of lithium bistriflimide (LiTFSI) in 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL) mixtures. We investigate conductivities, diffusion coefficients, solvation structures, and clustering behavior and verify our simulation model with experimental measurements available in literature and newly performed by us. Our results show that diffusion coefficients and conductivities are significantly influenced by the chain length of PS. The conductivity contribution of the short chains, like Li$_2$S$_4$, is lower than of longer PS chains, such as Li$_2$S$_6$ or Li$_2$S$_8$, despite the fact that the diffusion coefficient of Li$_2$S$_4$ is higher than for longer PS chains. The low conductivity of Li$_2$S$_4$ can be attributed to its low degree of dissociation and even to a formation of large clusters in the solution. It is also found that an addition of 1 M LiTFSI into PS solutions considerably reduces the clustering behavior. Our simulation model enables future systematic studies in various solvating and confining systems for the rational design of Li/S electrolytes.

physics.chem-ph↗

arXiv2020

Enhanced Catalytic Activity of Gold@Polydopamine Nanoreactors with Multi-compartment Structure Under NIR Irradiation

Photothermal conversion (PTC) nanostructures have great potential for applications in many fields, and therefore, they have attracted tremendous attention. However, the construction of a PTC nanoreactor with multi-compartment structure to achieve the combination of unique chemical properties and structural feature is still challenging due to the synthetic difficulties. Herein, we designed and synthesized a catalytically active, PTC gold (Au)@polydopamine (PDA) nanoreactor driven by infrared irradiation using assembled PS-b-P2VP nanosphere as soft template. The particles exhibit multi-compartment structure which is revealed by 3D electron tomography characterization technique. They feature permeable shells with tunable shell thickness. Full kinetics for the reduction reaction of 4-nitrophenol has been investigated using these particles as nanoreactors and compared with other reported systems. Notably, a remarkable acceleration of the catalytic reaction upon near-infrared irradiation is demonstrated, which reveals for the first time the importance of the synergistic effect of photothermal conversion and complex inner structure to the kinetics of the catalytic reduction. The ease of synthesis and fresh insights into catalysis will promote a new platform for novel nanoreactor studies.

physics.chem-ph↗

arXiv2018

Silver nanowires with optimized silica coating as versatile plasmonic resonators

Metal nanoparticles are the most frequently used nanostructures in plasmonics. However, besides nanoparticles, metal nanowires feature several advantages for applications. Their elongation offers a larger interaction volume, their resonances can reach higher quality factors, and their mode structure provides better coupling into integrated hybrid dielectric-plasmonic circuits. It is crucial though, to control the distance of the wire to a supporting substrate, to another metal layer or to active materials with sub-nanometer precision. A dielectric coating can be utilized for distance control, but it must not degrade the plasmonic properties. In this paper, we introduce a controlled synthesis and coating approach for silver nanowires to fulfill these demands. We synthesize and characterize silver nanowires of around 70 nm in diameter. These nanowires are coated with nm-sized silica shells using a modified Stöber method to achieve a homogeneous and smooth surface quality. We use transmission electron microscopy, dark-field microscopy and electron-energy loss spectroscopy to study morphology and plasmonic resonances of individual nanowires and quantify the influence of the silica coating. Thorough numerical simulations support the experimental findings showing that the coating does not deteriorate the plasmonic properties and thus introduce silver nanowires as usable building blocks for integrated hybrid plasmonic systems.

physics.optics↗

arXiv2018

Interaction of Proteins with Polyelectrolytes: A Comparison between Theory and Experiment

We discuss recent investigations of the interaction of polyelectrolytes with proteins. In particular, we review our recent studies on the interaction of simple proteins such as human serum albumin (HSA) or lysozyme with linear polyelectrolytes, charged dendrimers, charged networks, and polyelectrolyte brushes. In all cases discussed here we combined experimental work with molecular dynamics (MD) simulations and mean-field theories. In particular, isothermal titration calorimetry (ITC) has been employed to obtain the respective binding constants Kb and the Gibbs free energy of binding. MD-simulations with explicit counterions but implicit water demonstrate that counterion release is the main driving force for the binding of proteins to strongly charged polyelectrolytes: Patches of positive charges located on the surface of the protein become a multivalent counterion of the polyelectrolyte thereby releasing a number of counterions condensed on the polyelectrolyte. The binding Gibbs free energy due to counterion release is predicted to scale with the logarithm of the salt concentration in the system which is verified both by simulations and experiment. In several cases, namely for the interaction of proteins with linear polyelectrolytes and highly charged hydrophilic dendrimers the binding constant could be calculated from simulations in very good approximation. This finding demonstrated that in these cases explicit hydration effects do not contribute to the Gibbs free energy of binding. The Gibbs free energy can also be used to predict the kinetics of protein uptake by microgels for a given system by applying dynamic density functional theory.

cond-mat.soft↗

arXiv2018

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.

physics.chem-ph↗

arXiv2017

Counterion-release entropy governs the inhibition of serum proteins by polyelectrolyte drugs

Dendritic polyelectrolytes constitute high potential drugs and carrier systems for biomedical purposes, still their biomolecular interaction modes, in particular those determining the binding affinity to proteins, have not been rationalized. We study the interaction of the drug candidate dendritic polyglycerol sulfate (dPGS) with serum proteins using Isothermal Titration Calorimetry (ITC) interpreted and complemented with molecular computer simulations. Lysozyme is first studied as a well-defined model protein to verify theoretical concepts, which are then applied to the important cell adhesion protein family of selectins. We demonstrate that the driving force of the strong complexation originates mainly from the release of only a few condensed counterions from the dPGS upon binding. The binding constant shows a surprisingly weak dependence on dPGS size (and bare charge) which can be understood by colloidal charge-renormalization effects and by the fact that the magnitude of the dominating counterion-release mechanism almost exclusively depends on the interfacial charge structure of the protein-specific binding patch. Our findings explain the high selectivity of P- and L- selectins over E-selectin for dPGS to act as a highly anti-inflammatory drug. The entire analysis demonstrates that the interaction of proteins with charged polymeric drugs can be predicted by simulations with unprecedented accuracy. Thus, our results open new perspectives for the rational design of charged polymeric drugs and carrier systems.

cond-mat.soft↗

arXiv2017

Molecular simulations of electrolyte structure and dynamics in lithium-sulfur battery solvents

The performance of modern lithium-sulfur (Li/S) battery systems critically depends on the electrolyte and solvent compositions. For fundamental molecular insights and rational guidance of experimental developments, efficient and sufficiently accurate molecular simulations are thus in urgent need. Here, we construct a molecular dynamics (MD) computer simulation model of representative state-of-the art electrolyte-solvent systems for Li/S batteries constituted by lithium-bis(trifluoromethane)sulfonimide (LiTFSI) and LiNO3 electrolytes in mixtures of the organic solvents 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL). We benchmark and verify our simulations by comparing structural and dynamic features with various available experimental reference systems and demonstrate their applicability for a wide range of electrolyte-solvent compositions. For the state-of-the-art battery solvent, we finally calculate and discuss the detailed composition of the first lithium solvation shell, the temperature dependence of lithium diffusion, as well as the electrolyte conductivities and lithium transference numbers. Our model will serve as a basis for efficient future predictions of electrolyte structure and transport in complex electrode confinements for the optimization of modern Li/S batteries (and related devices).

physics.chem-ph↗

arXiv2017

Charged dendrimers revisited: Effective charge and surface potential of dendritic polyglycerol sulfate

We investigate key electrostatic features of charged dendrimers at hand of the biomedically important dendritic polyglycerol sulfate (dPGS) macromolecule using multi-scale computer simulations and Zetasizer experiments. In our simulation study, we first develop an effective mesoscale Hamiltonian specific to dPGS based on input from all-atom, explicit-water simulations of dPGS of low generation. Employing this in coarse-grained, implicit-solvent/explicit-salt Langevin dynamics simulations, we then study dPGS structural and electrostatic properties up to the sixth generation. By systematically mapping then the calculated electrostatic potential onto the Debye-Hückel form -- that serves as a basic defining equation for the effective charge -- we determine well-defined effective net charges and corresponding radii, surface charge densities, and surface potentials of dPGS. The latter are found to be up to one order of magnitude smaller than the bare values and consistent with previously derived theories on charge renormalization and weak saturation for high dendrimer generations (charges). Finally, we find that the surface potential of the dendrimers estimated from the simulations compare very well with our new electrophoretic experiments.

cond-mat.soft↗

arXiv2017

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.

cond-mat.soft↗

arXiv2016

Reaction rate of a composite core-shell nanoreactor with multiple, spatially distributed embedded nano-catalysts

We present a detailed theory for the total reaction rate constant of a composite core-shell nanoreactor, consisting of a central solid core surrounded by a hydrogel layer of variable thickness, where a given number of small catalytic nanoparticles are embedded at prescribed positions and are endowed with a prescribed surface reaction rate constant. Besides the precise geometry of the assembly, our theory accounts explicitly for the diffusion coefficients of the reactants in the hydrogel and in the bulk as well as for their transfer free energy jump upon entering the hydrogel shell. Moreover, we work out an approximate analytical formula for the overall rate constant, which is valid in the physically relevant range of geometrical and chemical parameters. We discuss in depth how the diffusion-controlled part of the rate depends on the essential variables, including the size of the central core. In particular, we derive some simple rules for estimating the number of nanocatalysts per nanoreactor for an efficient catalytic performance in the case of small to intermediate core sizes. Our theoretical treatment promises to provide a very useful and flexible tool for the design of superior performing nanoreactor geometries and with optimized nanoparticle load.

cond-mat.soft↗

arXiv2016

Thermosensitive Cu2O-PNIPAM core-shell nanoreactors with tunable photocatalytic activity

We report a facile and novel method for the fabrication of Cu2O@PNIPAM core-shell nanoreactors using Cu2O nanocubes as the core. The PNIPAM shell not only effectively protects the Cu2O nanocubes from oxidation, but also improves the colloidal stability of the system. The Cu2O@PNIPAM core-shell microgels can work efficiently as photocatalyst for the decomposition of methyl orange under visible light. A significant enhancement in the catalytic activity has been observed for the core-shell microgels compared with the pure Cu2O nanocubes. Most importantly, the photocatalytic activity of the Cu2O nanocubes can be further tuned by the thermosensitive PNIPAM shell, as rationalized by our recent theory.

physics.chem-ph↗

arXiv2015

Nonequilibrium Structure of Colloidal Dumbbells under Oscillatory Shear

We investigate the nonequilibrium behavior of dense, plastic-crystalline suspensions of mildly anisotropic colloidal hard dumbbells under the action of an oscillatory shear field by employing Brownian dynamics computer simulations. In particular, we extend previous investigations, where we uncovered novel nonequilibrium phase transitions, to other aspect ratios and to a larger nonequilibrium parameter space, that is, a wider range of strains and shear frequencies. We compare and discuss selected results in the context of novel scattering and rheological experiments. Both simulations and experiments demonstrate that the previously found transitions from the plastic crystal phase with increasing shear strain also occur at other aspect ratios. We explore the transition behavior in the strain-frequency phase and summarize it in a nonequilibrium phase diagram. Additionally, the experimental rheology results hint at a slowing down of the colloidal dynamics with higher aspect ratio.

cond-mat.soft↗

arXiv2015

Theory of Solvation-Controlled Reactions in Stimuli-Responsive Nanoreactors

Metallic nanoparticles embedded in stimuli-responsive polymers can be regarded as nanoreactors since their catalytic activity can be changed within wide limits: the physicochemical properties of the polymer network can be tuned and switched by external parameters, e.g. temperature or pH, and thus allows a selective control of reactant mobility and concentration close to the reaction site. Based on a combination of Debye's model of diffusion through an energy landscape and a two-state model for the polymer, here we develop an analytical expression for the observed reaction rate constant $k_{\rm obs}$. Our formula shows an exponential dependence of this rate on the solvation free enthalpy change $Δ\bar{G}_{\rm sol}$, a quantity which describes the partitioning of the reactant in the network versus bulk. Thus, changes in $Δ\bar{G}_{\rm sol}$, and not in the diffusion coefficient, will be the decisive factor affecting the reaction rate in most cases. A comparison with recent experimental data on switchable, thermosensitive nanoreactors demonstrates the general validity of the concept.

physics.chem-ph↗

arXiv2015

Interaction of Human Serum Albumin with short Polyelectrolytes: A study by Calorimetry and Computer Simulation

We present a comprehensive study of the interaction of human serum albumin (HSA) with poly(acrylic acid) (PAA; number average degree of polymerization: 25) in aqueous solution. The interaction of HSA with PAA is studied in dilute solution as the function of the concentration of added salt (20 - 100 mM) and temperature (25 - 37$^{\circ}$C). Isothermal titration calorimetry (ITC) is used to analyze the interaction and to determine the binding constant and related thermodynamic data. It is found that only one PAA chain is bound per HSA molecule. The free energy of binding $ΔG_b$ increases with temperature significantly. $ΔG_b$ decreases with increasing salt concentration and is dominated by entropic contributions due to the release of bound counterions. Coarse-grained Langevin computer simulations treating the counterions in an explicit manner are used study the process of binding in detail. These simulations demonstrate that the PAA chains are bound in the Sudlow II site of the HSA. Moreover, $ΔG_b$ is calculated from the simulations and found to be in very good agreement with the measured data. The simulations demonstrate clearly that the driving force of binding is the release of counterions in full agreement with the ITC-data.

cond-mat.soft↗

arXiv2014

Dynamic density functional theory of protein adsorption on polymer-coated nanoparticles

We present a theoretical model for the description of the adsorption kinetics of globular proteins onto charged core-shell microgel particles based on Dynamic Density Functional Theory (DDFT). This model builds on a previous description of protein adsorption thermodynamics [Yigit \textit{et al}, Langmuir 28 (2012)], shown to well interpret the available calorimetric experimental data of binding isotherms. In practice, a spatially-dependent free-energy functional including the same physical interactions is built, and used to study the kinetics via a generalised diffusion equation. To test this model, we apply it to the case study of Lysozyme adsorption on PNIPAM coated nanoparticles, and show that the dynamics obtained within DDFT is consistent with that extrapolated from experiments. We also perform a systematic study of the effect of various parameters in our model, and investigate the loading dynamics as a function of proteins' valence and hydrophobic adsorption energy, as well as their concentration and that of the nanoparticles. Although we concentrated here on the case of adsorption for a single protein type, the model's generality allows to study multi-component system, providing a reliable instrument for future studies of competitive and cooperative adsorption effects often encountered in protein adsorption experiments.

physics.bio-ph↗

arXiv2013

Colloidal gelation with variable attraction energy

We present an approximation scheme to the master kinetic equations for aggregation and gelation with thermal breakup in colloidal systems with variable attraction energy. With the cluster fractal dimension $d_{f}$ as the only phenomenological parameter, rich physical behavior is predicted. The viscosity, the gelation time and the cluster size are predicted in closed form analytically as a function of time, initial volume fraction and attraction energy by combining the reversible clustering kinetics with an approximate hydrodynamic model. The fractal dimension $d_{f}$ modulates the time evolution of cluster size, lag time and gelation time and of the viscosity. The gelation transition is strongly nonequilibrium and time-dependent in the unstable region of the state diagram of colloids where the association rate is larger than the dissociation rate. Only upon approaching conditions where the initial association and the dissociation rates are comparable for all species (which is a condition for the detailed balance to be satisfied) aggregation can occur with $d_{f}=3$. In this limit, homogeneous nucleation followed by Lifshitz-Slyozov coarsening is recovered. In this limited region of the state diagram the macroscopic gelation process is likely to be driven by large spontaneous fluctuations associated with spinodal decomposition.

cond-mat.soft↗

arXiv2012

Overshoots in stress strain curves: Colloid experiments and schematic mode coupling theory

The stress versus strain curves in dense colloidal dispersions under start-up shear flow are investigated combining experiments on model core-shell microgels, computer simulations of hard disk mixtures, and mode coupling theory. In dense fluid and glassy states, the transient stresses exhibit first a linear increase with the accumulated strain, then a maximum ('stress overshoot') for strain values around 5%, before finally approaching the stationary value, which makes up the flow curve. These phenomena arise in well-equilibrated systems and for homogeneous flows, indicating that they are generic phenomena of the shear-driven transient structural relaxation. Microscopic mode coupling theory (generalized to flowing states by integration through the transients) derives them from the transient stress correlations, which first exhibit a plateau (corresponding to the solid-like elastic shear modulus) at intermediate times, and then negative stress correlations during the final decay. We introduce and validate a schematic model within mode coupling theory which captures all of these phenomena and handily can be used to jointly analyse linear and large-amplitude moduli, flow curves, and stress-strain curves. This is done by introducing a new strain- and time-dependent vertex into the relation between the the generalized shear modulus and the transient density correlator.

cond-mat.soft↗