Serge Stoll

An improved OPLS–AA force field for carbohydrates

This work describes an improved version of the original OPLS–all atom (OPLS–AA) force field for carbohydrates (Damm et al., J Comp Chem 1997, 18, 1955). The improvement is achieved by applying additional scaling factors for the electrostatic interactions between 1,5‐ and 1,6‐interactions. This new model is tested first for improving the conformational energetics of 1,2‐ethanediol, the smallest polyol. With a 1,5‐scaling factor of 1.25 the force field calculated relative energies are in excellent agreement with the ab initio‐derived data. Applying the new 1,5‐scaling makes it also necessary to use a 1,6‐scaling factor for the interactions between the C4 and C6 atoms in hexopyranoses. After torsional parameter fitting, this improves the conformational energetics in comparison to the OPLS–AA force field. The set of hexopyranoses included in the torsional parameter derivation consists of the two anomers of D‐glucose, D‐mannose, and D‐galactose, as well as of the methyl‐pyranosides of D‐glucose, D‐mannose. Rotational profiles for the rotation of the exocyclic group and of different hydroxyl groups are also compared for the two force fields and at the ab initio level of theory. The new force field reduces the overly high barriers calculated using the OPLS–AA force field. This leads to better sampling, which was shown to produce more realistic conformational behavior for hexopyranoses in liquid simulation. From 10‐ns molecular dynamics (MD) simulations of α‐D‐glucose and α‐D‐galactose the ratios for the three different conformations of the hydroxymethylene group and the average 3JH,H coupling constants are derived and compared to experimental values. The results obtained for OPLS–AA–SEI force field are in good agreement with experiment whereas the properties derived for the OPLS–AA force field suffer from sampling problems. The undertaken investigations show that the newly derived OPLS–AA–SEI force field will allow simulating larger carbohydrates or polysaccharides with improved sampling of the hydroxyl groups.

Aggregation and disaggregation of ZnO nanoparticles: Influence of pH and adsorption of Suwannee River humic acid

The surface charge and average size of manufactured ZnO nanoparticles (NPs) were studied as a function of pH to understand the aggregation behavior and importance of the electrostatic interactions in solution. The interactions between ZnO and Suwannee River humic acid (SRHA) were then investigated under a range of environmentally relevant conditions with the ZnO nanoparticles pHPZC as the point of reference. The anionic charges carried by aquatic humic substances were found to play a major role in the aggregation and disaggregation of ZnO nanoparticles. At low concentrations of SRHA (<0.05 mg/L) and below the pHPZC, anionic SRHA was rapidly adsorbed onto the positively charged ZnO NPs hence promoting aggregation. With similar SHRA concentrations, at pHPZC, SRHA was able to control the suspension behavior of the ZnO and promote partial disaggregation in small volumes. This was more distinguishable when the pH was greater than pHPZC as SRHA formed a surface coating on the ZnO nanoparticles and enhanced stability via electrostatic and steric interactions. In most cases, the NP coating by SRHA induced disaggregation behavior in the ZnO nanoparticles and decreased the aggregate size in parallel to increasing SRHA concentrations. Results also suggest that environmental aquatic concentration ranges of humic acids largely modify the stability of aggregated or dispersed ZnO nanoparticles.

TiO2 nanoparticles aggregation and disaggregation in presence of alginate and Suwannee River humic acids. pH and concentration effects on nanoparticle stability

The behavior of manufactured TiO2 nanoparticles is studied in a systematic way in presence of alginate and Suwannee River humic acids at variable concentrations. TiO2 nanoparticles aggregation, disaggregation and stabilization are investigated using dynamic light scattering and electrophoretic experiments allowing the measurement of z-average hydrodynamic diameters and zeta potential values. Stability of the TiO2 nanoparticles is discussed by considering three pH-dependent electrostatic scenarios. In the first scenario, when pH is below the TiO2 nanoparticle point of zero charge, nanoparticles exhibit a positively charged surface whereas alginate and Suwannee River humic acids are negatively charged. Fast adsorption at the TiO2 nanoparticles occurs, promotes surface charge neutralization and aggregation. By increasing further alginate and Suwannee River humic acids concentrations charge inversion and stabilization of TiO2 nanoparticles are obtained. In the second electrostatic scenario, at the surface charge neutralization pH, TiO2 nanoparticles are rapidly forming aggregates. Adsorption of alginate and Suwannee River humic acids on aggregates leads to their partial fragmentation. In the third electrostatic scenario, when nanoparticles, alginate and Suwannee River humic acids are negatively charged, only a small amount of Suwannee River humic acids is adsorbed on TiO2 nanoparticles surface. It is found that the fate and behavior of individual and aggregated TiO2 nanoparticles in presence of environmental compounds are mainly driven by the complex interplay between electrostatic attractive and repulsive interactions, steric and van der Waals interactions, as well as concentration ratio. Results also suggest that environmental aquatic concentration ranges of humic acids and biopolymers largely modify the stability of aggregated or dispersed TiO2 nanoparticles.

Polyelectrolyte adsorption on charged particles: Ionic concentration and particle size effects—A Monte Carlo approach

The complexation between a charged polymer and an oppositely charged spherical particle is investigated using Monte Carlo simulations. Electrostatic interactions are described in the Debye–Huckel approximation. The influence of particle size and ionic concentration on the adsorption/desorption limit, interfacial structure of the adsorbed layer, amount of adsorbed polymer, and the overcharging issue is investigated. Attention is focused on polyelectrolyte adsorption on small spherical particles whose surface curvature effects are expected to limit the amount of adsorbed monomers, large particles that allow the polyelectrolyte to spread to the same extent as on a flat surface, and particles whose radius is close to the polyelectrolyte radius of gyration so that the chain can completely wrap around it. The formation of a polyelectrolyte/particle complex and the conformations of the adsorbed polyelectrolyte are found to result from two competing effects: the electrostatic repulsions between the chain monomers...

Heterogeneity and Persistence Length in Human Ocular Mucins

Atomic force microscopy (AFM) has been used to investigate the heterogeneity and flexibility of human ocular mucins and their subunits. We have paid particular attention, in terms of theory and experiment, to the problem of inducing the polymers to assume equilibrium conformations at a surface. Mucins deposited from a buffer containing Ni(2+) ions adopt extended conformations on mica akin to those observed for DNA under similar conditions. The heterogeneity of the intracellular native mucins is evident from a histogram of contour lengths, reflecting, in part, the diversity of mucin gene products expressed. Reduction of the native mucin with dithiothreitol, thereby breaking the S==S bonds between cysteine residues, causes a marked reduction in polymer length. These results reflect the modes of transport and assembly of newly synthesized mucins in vivo. By modifying the worm-like chain model for applicability to two dimensions, we have confirmed that under the conditions employed mucin adsorbs to mica in an equilibrated conformation. The determined persistence length of the native mucin, 36 nm, is consistent with that of an extended, flexible polymer; such characteristics will influence the properties of the gels formed in vivo.

Monte Carlo simulations of hydrophobic polyelectrolytes: Evidence of complex configurational transitions

Off-lattice Monte Carlo simulations, including electrostatic and Lennard-Jones potentials, are performed to investigate at the limit of counterion condensation the dilute conformations of quenched polymer chains in poor solvent conditions. The Monte Carlo (MC) search procedure is improved to achieve dense conformations in the limit of both strong attractive and repulsive interaction potentials. Configurational properties such as the radius of gyration, and single chain structure factors are calculated as a function of attractive monomer–monomer interactions, ionic concentration, and monomer number. It is observed that hydrophobic polyelectrolytes exhibit a large variety of conformations compared to flexible or semiflexible polyelectrolytes without hydrophobic groups. MC results demonstrate that there is a range of electrolyte concentration and hydrophobicity for which polymers exhibit exotic but stable conformations, namely the pearl necklace and the cigar-shape conformation. It is shown that by gradually...

Towards a better understanding on agglomeration mechanisms and thermodynamic properties of TiO2 nanoparticles interacting with natural organic matter

Interaction between engineered nanoparticles and natural organic matter is investigated by measuring the exchanged heat during binding process with isothermal titration calorimetry. TiO2 anatase nanoparticles and alginate are used as engineered nanoparticles and natural organic matter to get an insight into the thermodynamic association properties and mechanisms of adsorption and agglomeration. Changes of enthalpy, entropy and total free energy, reaction stoichiometry and affinity binding constant are determined or calculated at a pH value where the TiO2 nanoparticles surface charge is positive and the alginate exhibits a negative structural charge. Our results indicate that strong TiO2-alginate interactions are essentially entropy driven and enthalpically favorable with exothermic binding reactions. The reaction stoichiometry and entropy gain are also found dependent on the mixing order. Finally correlation is established between the binding enthalpy, the reaction stoichiometry and the zeta potential values determined by electrophoretic mobility measurements. From these results two types of agglomeration mechanisms are proposed depending on the mixing order. Addition of alginate in TiO2 dispersions is found to form agglomerates due to polymer bridging whereas addition of TiO2 in alginate promotes a more individually coating of the nanoparticles.

Effect of electrolyte valency, alginate concentration and pH on engineered TiO2 nanoparticle stability in aqueous solution

Agglomeration and disagglomeration processes are expected to play a key role on the fate of engineered nanoparticles in natural aquatic systems. These processes are investigated here in detail by studying first the stability of TiO2 nanoparticles in the presence of monovalent and divalent electrolytes at different pHs (below and above the point of zero charge of TiO2) and discussing the importance of specific divalent cation adsorption with the help of the DLVO theory as well as the importance of the nature of the counterions. Then the impact of one polysaccharide (alginate) on the stability of agglomerates formed under pH and water hardness representative of Lake Geneva environmental conditions is investigated. In these conditions the large TiO2 agglomerates (diameter>1μm) are positively charged due to Ca(2+) and Mg(2+) specific adsorption and alginate, which is negatively charged, adsorbs onto the agglomerate surface. Our results indicate that the presence of alginate at typical natural organic matter concentration (1-10 mg L(-1)) strongly modifies the TiO2 agglomerate (50 mg L(-1)) stability by inducing their partial and rapid disagglomeration. The importance of disagglomeration is found dependent on the alginate concentration with maximum of disagglomeration obtained for alginate concentration ≥8 mg L(-1) and leading to 400 nm fragments. From an environmental point of view partial restabilization of TiO2 agglomerates in the presence of alginate constitutes an important outcome. Disagglomeration will enhance their transport and residence time in aquatic systems which is an important step in the current knowledge on risk assessment associated to engineered nanoparticles.

Adsorption of Weak Polyelectrolytes on Charged Nanoparticles. Impact of Salt Valency, pH, and Nanoparticle Charge Density. Monte Carlo Simulations

Complex formation between a weak flexible polyelectrolyte chain and one positively charged nanoparticle in presence of explicit counterions and salt particles is investigated using Monte Carlo simulations. The influence of parameters such as the nanoparticle surface charge density, salt valency, and solution property such as the pH on the chain protonation/deprotonation process and monomer adsorption at the nanoparticle surface are systematically investigated. It is shown that the nanoparticle presence significantly modifies chain acid/base and polyelectrolyte conformational properties. The importance of the attractive electrostatic interactions between the chain and the nanoparticle clearly promotes the chain deprotonation leading, at high pH and nanoparticle charge density, to fully wrapped polyelectrolyte at the nanoparticle surface. When the nanoparticle bare charge is overcompensated by the polyelectrolyte charges, counterions and salt particles condense at the surface of the polyelectrolyte-nanoparticle complex to compensate for the excess of charges providing from the adsorbed polyelectrolyte chain. It is also shown that the complex formation is significantly affected by the salt valency. Indeed, with the presence of trivalent salt cations, competition is observed between the nanoparticle and the trivalent cations. As a result, the amount of adsorbed monomers is less important than in the monovalent and divalent case and chain conformations are different due to the collapse of polyelectrolyte segments around trivalent cations out of the nanoparticle adsorption layer.

Titration of hydrophobic polyelectrolytes using Monte Carlo simulations

The conformation and titration curves of weak (or annealed) hydrophobic polyelectrolytes have been examined using Monte Carlo simulations with screened Coulomb potentials in the grand canonical ensemble. The influence of the ionic concentration pH and presence of hydrophobic interactions has been systematically investigated. A large number of conformations such as extended, pearl-necklace, cigar-shape, and collapsed structures resulting from the subtle balance of short-range hydrophobic attractive interactions and long-range electrostatic repulsive interactions between the monomers have been observed. Titration curves were calculated by adjusting the pH-pK(0) values (pK(0) represents the intrinsic dissociation constant of an isolated monomer) and then calculating the ionization degree alpha of the polyelectrolyte. Important transitions related to cascades of conformational changes were observed in the titration curves, mainly at low ionic concentration and with the presence of strong hydrophobic interactions. We demonstrated that the presence of hydrophobic interactions plays an important role in the acid-base properties of a polyelectrolyte in promoting the formation of compact conformations and hence decreasing the polyelectrolyte degree of ionization for a given pH-pK(0) value.