arXiv subjects

Joachim Dzubiella

Publications and source records attributed to Joachim Dzubiella.

At least 37 records · Page 2Linked to original sources

arXiv2021

Controlling Solvent Quality by Time: Self-Avoiding Sprints in Nonequilibrium Polymerization

A fundamental paradigm in polymer physics is that macromolecular conformations in equilibrium can be described by universal scaling laws, being key for structure, dynamics, and function of soft (biological) matter and in the materials sciences. Here, we reveal that during diffusion-influenced, nonequilibrium chain-growth polymerization, scaling laws change qualitatively, in particular, the growing polymers exhibit a surprising self-avoiding walk (SAW) behavior in poor and theta-solvents. Our analysis, based on monomer-resolved reaction-diffusion computer simulations, demonstrates that this phenomenon is a result of i) nonequilibrium monomer density depletion correlations around the active polymerization site, leading to a locally directed and self-avoiding growth, in conjunction with ii) chain (Rouse) relaxation times larger than the competing polymerization reaction time. These intrinsic nonequilibrium mechanisms are facilitated by fast and persistent reaction-driven diffusion (sprints) of the active site, with analogies to pseudo-chemotactic active Brownian particles. Our findings have implications for time-controlled structure formation in polymer processing, as in, e.g., reactive self-assembly, photo-crosslinking, and 3D printing.

cond-mat.soft↗

arXiv2021

Transport in polymer membranes beyond linear response: Controlling permselectivity by the driving force

In the popular solution-diffusion picture, the membrane permeability is defined as the product of the partition ratio and the diffusivity of penetrating solutes inside the membrane in the linear response regime, i.e., in equilibrium. However, of practical importance is the penetrants' flux across the membrane driven by external forces. Here, we study nonequilibrium membrane permeation orchestrated by a uniform external driving field using molecular computer simulations and continuum (Smoluchowski) theory in the stationary state. In the simulations, we explicitly resolve the penetrants' transport across a finite monomer-resolved polymer network, addressing one-component penetrant systems and mixtures. We introduce and discuss possible definitions of nonequilibrium, force-dependent permeability, representing `system' and `membrane' permeability. In particular, we present for the first time a definition of the differential permeability response to the force. We demonstrate that the latter turns out to be significantly nonlinear for low-permeable systems, leading to a high amount of selectiveness in permeability, called `permselectivity', and is tunable by the driving force. Our continuum-level analytical solutions exhibit remarkable qualitative agreement with the penetrant- and polymer-resolved simulations, thereby allowing us to characterize the underlying mechanism of permeabilities and steady-state transport beyond the linear response level.

cond-mat.soft↗

arXiv2021

Electrostatic reaction inhibition in nanoparticle catalysis

Electrostatic reaction inhibition in heterogeneous catalysis emerges if charged reactants and products are adsorbed on the catalyst and thus repel the approaching reactants. In this work, we study the effects of electrostatic inhibition on the reaction rate of unimolecular reactions catalyzed on the surface of a spherical model nanoparticle by using particle-based reaction-diffusion simulations. Moreover, we derive closed rate equations based on approximate Debye-Smoluchowski rate theory, valid for diffusion-controlled reactions, and a modified Langmuir adsorption isotherm, relevant for reaction-controlled reactions, to account for electrostatic inhibition in the Debye-Hückel limit. We study the kinetics of reactions ranging from low to high adsorptions on the nanoparticle surface and from the surface- to diffusion-controlled limits for charge valencies 1 and 2. In the diffusion-controlled limit, electrostatic inhibition drastically slows down the reactions for strong adsorption and low ionic concentration, which is well described by our theory. In particular, the rate decreases with adsorption affinity, because in this case the inhibiting products are generated at high rate. In the (slow) reaction-controlled limit, the effect of electrostatic inhibition is much weaker, as semi-quantitatively reproduced by our electrostatic-modified Langmuir theory. We finally propose and verify a simple interpolation formula that describes electrostatic inhibition for all reaction speeds (`diffusion-influenced' reactions) in general.

physics.chem-ph↗

arXiv2021

Highly Heterogeneous Polarization and Solvation of Gold Nanoparticles in Aqueous Electrolytes

The performance of gold nanoparticles (NPs) in applications depends critically on the structure of the NP-solvent interface, at which the electrostatic surface polarization is one of the key characteristics that affects hydration, ionic adsorption, and electrochemical reactions. Here, we demonstrate significant effects of explicit metal polarizability on the solvation and electrostatic properties of bare gold NPs in aqueous electrolyte solutions of sodium salts of various anions (Cl$^-$, BF$_4$$^-$, PF$_6$$^-$, Nip$^-$(nitrophenolate), and 3- and 4-valent hexacyanoferrate (HCF)), using classical molecular dynamics simulations with a polarizable core-shell model of the gold atoms. We find considerable spatial heterogeneity of the polarization and electrostatic potentials on the NP surface, mediated by a highly facet-dependent structuring of the interfacial water molecules. Moreover, ion-specific, facet-dependent ion adsorption leads to large alterations of the interfacial polarization. Compared to non-polarizable NPs, polarizability modifies water local dipole densities only slightly, but has substantial effects on the electrostatic surface potentials, and leads to significant lateral redistributions of ions on the NP surface. Besides, interfacial polarization effects on the individual monovalent ions cancel out in the far field, and effective Debye-Hückel surface potentials remain essentially unaffected, as anticipated from continuum `image-charge' concepts. Hence, the explicit charge response of metal NPs is crucial for the accurate description and interpretation of interfacial electrostatics (as, e.g., for charge transfer and interface polarization in catalysis and electrochemistry).

physics.chem-ph↗

arXiv2020

Structure and dynamics of responsive colloids with dynamical polydispersity

Dynamical polydispersity in single-particle properties, for example a fluctuating particle size, shape, charge density, etc., is intrinsic to responsive colloids (RCs), such as biomacromolecules or microgels, but is typically not resolved in coarse-grained mesoscale simulations. Here, we present Brownian Dynamics (BD) simulations of suspensions of RCs modeling soft hydrogel colloids, for which the size of the individual particles is an explicitly resolved (Gaussian) degree of freedom and dynamically responds to the local interacting environment. We calculate the liquid structure, emergent size distributions, long-time diffusion, and property (size) relaxation kinetics for a wide range of densities and intrinsic property relaxation times in the canonical ensemble. Comparison to interesting reference cases, such as conventional polydisperse suspensions with a frozen parent distribution, or conventional monodisperse systems interacting with an effective pair potential for one fixed size, shows a significant spread in the structure and dynamics. The differences, most apparent in the high density regimes, are due to many-body correlations and the dynamical coupling between property and translation in RC systems, not explicitly accounted for in the conventional treatments. In particular, the translational diffusion in the RC systems is surprisingly close to the free (single RC) diffusion, mainly due to a cancellation of crowding and size compression effects. We show that an effective monodisperse pair potential can be constructed that describes the many-body correlations reasonably well by convoluting the RC pair potential with the density-dependent emergent size distributions and using a mean effective diffusion constant.

cond-mat.soft↗

arXiv2020

Guanidinium can both Cause and Prevent the Hydrophobic Collapse of Biomacromolecules

A combination of Fourier transform infrared and phase transition measurements as well as molecular computer simulations, and thermodynamic modeling were performed to probe the mechanisms by which guanidinium salts influence the stability of the collapsed versus uncollapsed state of an elastin-like polypeptide (ELP), an uncharged thermoresponsive polymer. We found that the cation's action was highly dependent upon the counteranion with which it was paired. Specifically, Gnd+ was depleted from the ELP/water interface and was found to stabilize the collapsed state of the macromolecule when paired with well-hydrated anions such as sulfate. Stabilization in this case occurred via an excluded volume (or depletion) effect, whereby sulfate was strongly partitioned away from the ELP/water interface. Intriguingly, at low salt concentrations, Gnd+ was also found to stabilize the collapsed state of the ELP when paired with SCN-, which is a strong binder for the ELP. In this case, the anion and cation were both found to be enriched in the collapsed state of the polymer. The collapsed state was favored because the Gnd+ crosslinked the polymer chains together. Moreover, the anion helped partition Gnd+ to the polymer surface. At higher salt concentrations (>1.5 M), GndSCN switched to stabilizing the uncollapsed state because a sufficient amount of Gnd+ and SCN- partitioned to the polymer surface to prevent cross-linking from occurring. Finally, in a third case, it was found that salts which interacted in an intermediate fashion with the polymer (e.g. GndCl) favored the uncollapsed conformation at all salt concentrations.

cond-mat.soft↗

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

Ionic structure around polarizable metal nanoparticles in aqueous electrolytes

Metal nanoparticles are receiving increased scientific attention owing to their unique physical and chemical properties that make them suitable for a wide range of applications in diverse fields, such as electrochemistry, biochemistry, and nanomedicine. Their high metallic polarizability is a crucial determinant that defines their electrostatic character in various electrolyte solutions. Here, we introduce a continuum-based model of a metal nanoparticle with explicit polarizability in the presence of different kinds of electrolytes. We employ several, variously sophisticated, theoretical approaches, corroborated by Monte Carlo simulations in order to elucidate the basic electrostatics principles of the model. We investigate how different kinds of asymmetries between the ions result in non-trivial phenomena, such as charge separation and a build-up of a so-called zero surface-charge double layer.

physics.chem-ph↗

arXiv2020

Coverage Fluctuations and Correlations in Nanoparticle-Catalyzed Diffusion-Influenced Bimolecular Reactions

The kinetic processes in nanoparticle-based catalysis are dominated by large fluctuations and spatiotemporal heterogeneities, in particular for diffusion-influenced reactions which are far from equilibrium. Here, we report results from particle-resolved reaction-diffusion simulations of steady-state bimolecular reactions catalyzed on the surface of a single, perfectly spherical nanoparticle. We study various reactant adsorption and diffusion regimes, in particular considering the crowding effects of the reaction products. Our simulations reveal that fluctuations, significant coverage cross-correlations, transient self-poisoning, related domain formation, and excluded-volume effects on the nanoparticle surface lead to a complex kinetic behavior, sensitively tuned by the balance between adsorption affinity, mixed 2D and 3D diffusion, and chemical reaction propensity. The adsorbed products are found to influence the correlations and fluctuations, depending on overall reaction speed, thereby going beyond conventional steric (e.g., Langmuir-like) product inhibition mechanisms. We summarize our findings in a state diagram depicting the nonlinear kinetic regimes by an apparent surface reaction order in dependence of the intrinsic reaction propensity and adsorption strength. Our study using a simple, perfectly spherical, and inert nanocatalyst demonstrates that spatiotemporal heterogeneities are intrinsic to the reaction-diffusion problem and not necessarily caused by any dynamical surface effects from the catalyst (e.g., dynamical surface reconstruction), as often argued.

physics.chem-ph↗

arXiv2020

Affinity, Kinetics, and Pathways of Anisotropic Ligands Binding to Hydrophobic Model Pockets

Using explicit-water molecular dynamics (MD) simulations of a generic pocket-ligand model we investigate how chemical and shape anisotropy of small ligands influences the affinities, kinetic rates and pathways for their association to hydrophobic binding sites. In particular, we investigate aromatic compounds, all of similar molecular size, but distinct by various hydrophilic or hydrophobic residues. We demonstrate that the most hydrophobic sections are in general desolvated primarily upon binding to the cavity, suggesting that specific hydration of the different chemical units can steer the orientation pathways via a `hydrophobic torque'. Moreover, we find that ligands with bimodal orientation fluctuations have significantly increased kinetic barriers for binding compared to the kinetic barriers previously observed for spherical ligands due to translational fluctuations. We exemplify that these kinetic barriers, which are ligand specific, impact both binding and unbinding times for which we observe considerable differences between our studied ligands.

cond-mat.soft↗

arXiv2020

Structure and position-dependent properties of inhomogeneous suspensions of responsive colloids

Responsive particles, such as biomacromolecules or hydrogels, display a broad and polymodal distribution of conformations and have thus the ability to change their properties (e.g, size, shape, charge density, etc.) substantially in response to external fields or to their local environment (e.g., mediated by cosolutes or pH). Here, we discuss the basic statistical mechanics for a model of responsive colloids (RCs) by introducing an additional property degree of freedom as a collective variable in a formal coarse-graining procedure. The latter leads to an additional one-body term in the coarse-grained (CG) free energy, defining a single-particle property distribution for an individual polydisperse RC. We argue that in the equilibrium thermodynamic limit such a CG system of RCs behaves like a conventional polydisperse system of non-responsive particles. We then illustrate the action of external fields, which impose local (position-dependent) property distributions leading to non-trivial effects on the spatial one-body property and density profiles, even for an ideal (non-interacting) gas of RCs. We finally apply density functional theory in the local density approximation (LDA-DFT) to discuss the effects of particle interactions for specific examples of i) a suspension of RCs in an external field linear in both position and property, ii) a suspension of RCs with highly localized properties (sizes) confined between two walls, and iii) a two-component suspension where an inhomogeneously distributed (non-responsive) cosolute component, as found, e.g., in the studies of osmolyte- or salt-induced collapse/swelling transitions of thermosensitive polymers, modifies the local properties and density of the RC liquid.

cond-mat.soft↗

arXiv2020

Ion-specific Adsorption on Bare Gold (Au) Nanoparticles in Aqueous Solution: Double-Layer Structure and Surface Potentials

We study the solvation and electrostatic properties of bare gold (Au) nanoparticles (NPs) of $1$-$2$ nm in size in aqueous electrolyte solutions of sodium salts of various anions with large physicochemical diversity (Cl$^-$, BF$_4$$^-$, PF$_6$$^-$, Nip$^-$(nitrophenolate), 3- and 4-valent hexacyanoferrate (HCF)) using nonpolarizable, classical molecular dynamics computer simulations. We find a substantial facet selectivity in the adsorption structure and spatial distribution of the ions at the Au-NPs: while sodium and some of the anions (e.g., Cl$^-$, HCF$^{3-}$) adsorb more at the `edgy' (100) and (110) facets of the NPs, where the water hydration structure is more disordered, other ions (e.g., BF$_4$$^-$, PF$_6$$^-$, Nip$^-$) prefer to adsorb strongly on the extended and rather flat (111) facets. In particular, Nip$^-$, which features an aromatic ring in its chemical structure, adsorbs strongly and perturbs the first water monolayer structure on the NP (111) facets substantially. Moreover, we calculate adsorptions, radially-resolved electrostatic potentials, as well as the far-field effective electrostatic surface charges and potentials by mapping the long-range decay of the calculated electrostatic potential distribution onto the standard Debye-Hückel form. We show how the extrapolation of these values to other ionic strengths can be performed by an analytical Adsorption-Grahame relation between effective surface charge and potential. We find for all salts negative effective surface potentials in the range from $-10$ mV for NaCl down to about $-80$ mV for NaNip, consistent with typical experimental ranges for the zeta-potential. We discuss how these values depend on the surface definition and compare them to the explicitly calculated electrostatic potentials near the NP surface, which are highly oscillatory in the $\pm 0.5$ V range.

physics.chem-ph↗

arXiv2020

Thermal compaction of disordered and elastin-like polypeptides: a temperature-dependent, sequence-specific coarse-grained simulation model

Elastin-like polypeptides (ELPs) undergo a sharp solubility transition from low temperature solvated phases to coacervates at elevated temperatures, driven by the increased strength of hydrophobic interactions at higher temperatures. The transition temperature, or 'cloud point', critically depends on sequence composition, sequence length, and concentration of the ELPs. In this work, we present a temperature-dependent, implicit solvent, sequence-specific coarse-grained (CG) simulation model that reproduces the transition temperatures as a function of sequence length and guest residue identity of various experimentally probed ELPs to appreciable accuracy. Our model builds upon the self-organized polymer model introduced recently for intrinsically disordered polypeptides (SOP-IDP), and introduces a semi-empirical functional form for the temperature-dependence of hydrophobic interactions. In addition to the fine performance for various ELPs, we demonstrate the ability of our model to capture the thermal compactions in dominantly hydrophobic intrinsically disordered polypeptides (IDPs), consistent with experimental scattering data. With the high computational efficiency afforded by the CG representation, we envisage that the model will be ideally suited for simulations of large-scale structures such as ELP networks and hydrogels, as well as agglomerates of IDPs.

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

Competitive sorption of mono- versus di-valent ions by highly charged globular macromolecules

When a highly charged globular macromolecule, such as a dendritic polyelectrolyte or charged nanogel, is immersed into a physiological electrolyte solution, monovalent and divalent counterions from the solution bind to the macromolecule in a certain ratio and thereby almost completely electroneutralize it. For charged macromolecules in biological media, the number ratio of bound mono- versus di-valent ions is decisive for the desired function. A theoretical prediction of such a sorption ratio is challenging because of the competition of electrostatic (valency), ion-specific, and binding saturation effects. Here, we devise and discuss a few approximate models to predict such an equilibrium sorption ratio by extending and combining established electrostatic binding theories such as Donnan, Langmuir, Manning as well as Poisson-Boltzmann approaches, to systematically study the competitive uptake of mono- and di-valent counterions by the macromolecule. We compare and fit our models to coarse-grained (implicit-solvent) computer simulation data of the globular polyelectrolyte dendritic polyglycerol sulfate (dPGS) in salt solutions of mixed valencies. The dPGS has high potential to serve in macromolecular carrier applications in biological systems and at the same time constitutes a good model system for a highly charged macromolecule. We finally use the simulation-informed models to extrapolate and predict electrostatic features such as the effective charge as a function of the divalent ion concentration for a wide range of dPGS generations (sizes).

cond-mat.soft↗

arXiv2020

Tuning the Selective Permeability of Polydisperse Polymer Networks

We study the permeability and selectivity (`permselectivity') of model membranes made of polydisperse polymer networks for molecular penetrant transport, using coarse-grained, implicit-solvent computer simulations. The permeability $\mathcal P$ is determined on the linear-response level using the solution-diffusion model, $\mathcal P = {\mathcal K}D_\text{in}$, $\textit{i.e.}$, by calculating the equilibrium penetrant partition ratio $\mathcal K$ and penetrant diffusivity $D_\text{in}$ inside the membrane. We vary two key parameters, namely the monomer-monomer interaction, which controls the degree of swelling and collapse of the network, and the monomer-penetrant interaction, which tunes the penetrant uptake and microscopic energy landscape for diffusive transport. The results for the partition ratio $\mathcal K$ cover four orders of magnitude and are non-monotonic versus the parameters, which is well interpreted by a second-order virial expansion of the free energy of transferring one penetrant from bulk into the polymeric medium. We find that the penetrant diffusivity $D_\text{in}$ in the polydisperse networks, in contrast to highly ordered membrane structures, exhibits relatively simple exponential decays and obeys well-known free-volume and Kramers' escape scaling laws. The eventually resulting permeability $\mathcal P$ thus resembles the qualitative functional behavior (including maximization and minimization) of the partitioning. However, partitioning and diffusion are anti-correlated, yielding large quantitative cancellations, controlled and fine-tuned by the network density and interactions as rationalized by our scaling laws. As a consequence, we finally demonstrate that even small changes of penetrant-network interactions, $\textit{e.g.}$, by half a $k_\text{B}T$, modify the permselectivity of the membrane by almost one order of magnitude.

cond-mat.soft↗

arXiv2020

Controlling the microstructure and phase behavior of confined soft colloids by active interaction switching

We explore the microstructure and phase behavior of confined soft colloids which can actively switch their interactions at a predefined kinetic rate. For this, we employ a reaction-diffusion approach based on a reactive dynamical density-functional theory (R-DDFT) and study the effect of a binary (two-state) switching of the size of colloids interacting with a Gaussian pair potential. The rate of switching interpolates between a near-equilibrium binary Gaussian mixture at low rates and an effective monodisperse liquid for large rates, hence strongly affecting the one-body density profiles, adsorption, and pressure at confining walls. Importantly, we demonstrate that sufficiently fast switching impedes the phase separation of an (in equilibrium) unstable liquid, allowing the dynamic control of the degree of mixing/condensation and local micro-structuring in a cellular confinement by tuning the switching rate.

cond-mat.soft↗

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↗