Surfactant adsorption and aggregate structure at silica nanoparticles: Effects of particle size and surface modification

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.The influence of particle size and a surface modifier on the self-assembly of the nonionic surfactant C12E5 at silica nanoparticles was studied by adsorption measurements and small-angle neutron scattering (SANS). Silica nanoparticles of diameter 13 to 43 nm were synthesized involving the basic amino acid lysine. A strong decrease of the limiting adsorption of C12E5 with decreasing particle diameter was found. To unveil the role of lysine as a surface modifier for the observed size dependence of surfactant adsorption, the morphology of the surfactant aggregates assembled on pure siliceous nanoparticles (Ludox-TMA, 27 nm) and their evolution with increasing lysine concentration at a fixed surfactant-to-silica ratio was studied by SANS. In the absence of lysine, the surfactant forms surface micelles at silica particles. As the concentration of lysine is increased, a gradual transition from the surface micelles to detached wormlike micelles in the bulk solution is observed. The changes in surfactant aggregate morphology cause pronounced changes of the system properties, as is demonstrated by turbidity measurements as a function of temperature. These findings are discussed in terms of particle surface curvature and surfactant binding strength, which present new insight into the delicate balance between the two properties.EC/FP7/226507/EU/Integrated Infrastructure Initiative for Neutron Scattering and Muon Spectroscopy/NMI3DFG, GRK 1524, Self-Assembled Soft-Matter Nanostructures at Interface

Bridging interactions of proteins with silica nanoparticles: The influence of pH, ionic strength and protein concentration

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Charge-driven bridging of nanoparticles by macromolecules represents a promising route for engineering functional structures, but the strong electrostatic interactions involved when using conventional polyelectrolytes impart irreversible complexation and ill-defined structures. Recently it was found that the electrostatic interaction of silica nanoparticles with small globular proteins leads to aggregate structures that can be controlled by pH. Here we study the combined influence of pH and electrolyte concentration on the bridging aggregation of silica nanoparticles with lysozyme in dilute aqueous dispersions. We find that protein binding to the silica particles is determined by pH irrespective of the ionic strength. The hetero-aggregate structures formed by the silica particles with the protein were studied by small-angle X-ray scattering (SAXS) and the structure factor data were analyzed on the basis of a short-range square-well attractive pair potential (close to the sticky-hard-sphere limit). It is found that the electrolyte concentration has a strong influence on the stickiness near pH 5, where the weakly charged silica particles are bridged by the strongly charged protein. An even stronger influence of the electrolyte is found in the vicinity of the isoelectric point of the protein (pI = 10.7) and is attributed to shielding of the repulsion between the highly charged silica particles and hydrophobic interactions between the bridging protein molecules.DFG, GRK 1524, Self-Assembled Soft-Matter Nanostructures at Interface

Surface Aggregate Structure of Nonionic Surfactants on Silica Nanoparticles

The self-assembly of two nonionic surfactants, pentaethylene glycol monododecyl ether (C12E5) and n-dodecyl-{\ss}-maltoside ({\ss}-C12G2), in the presence of a purpose-synthesized silica sol of uniform particle size (diameter 16 nm) has been studied by adsorption measurements, dynamic light scattering and small-angle neutron scattering (SANS) using a H2O/D2O mixture matching the silica, in order to highlight the structure of the surfactant aggregates. For C12E5 strong aggregative adsorption onto the silica beads, with a high plateau value of the adsorption isotherm above the CMC was found. SANS measurements were made at a series of loadings, from zero surfactant up to maximum surface coverage. It is found that the spherical core-shell model nicely reproduces the SANS data up to and including the local maximum at q = 0.42 nm-1 but not in the Porod region of high q, indicating that the surface area of the adsorbed surfactant is underestimated by the model of a uniform adsorbed layer. A satisfactory representation of the entire scattering profiles is obtained with the model of micelle-decorated silica beads, indicating that C12E5 is adsorbed as spherical micellar aggregates. This behaviour is attributed to the high surface curvature of the silica which prevents an effective packing of the hydrophobic chains of the amphiphile in a bilayer configuration. For the maltoside surfactant {\ss}-C12G2 very weak adsorption on the silica beads was found. The SANS profile indicates that this surfactant forms oblate ellipsoidal micelles in the silica dispersion, as in the absence of the silica beads

Surface induced disorder in body-centered cubic alloys

We present Monte Carlo simulations of surface induced disordering in a model of a binary alloy on a bcc lattice which undergoes a first order bulk transition from the ordered DO3 phase to the disordered A2 phase. The data are analyzed in terms of an effective interface Hamiltonian for a system with several order parameters in the framework of the linear renormalization approach due to Brezin, Halperin and Leibler. We show that the model provides a good description of the system in the vicinity of the interface. In particular, we recover the logarithmic divergence of the thickness of the disordered layer as the bulk transition is approached, we calculate the critical behavior of the maxima of the layer susceptibilities, and demonstrate that it is in reasonable agreement with the simulation data. Directly at the (110) surface, the theory predicts that all order parameters vanish continuously at the surface with a nonuniversal, but common critical exponent. However, we find different exponents for the order parameter of the DO3 phase and the order parameter of the B2 phase. Using the effective interface model, we derive the finite size scaling function for the surface order parameter and show that the theory accounts well for the finite size behavior of the DO3 ordering but not for that of B2 ordering. The situation is even more complicated in the neighborhood of the (100) surface, due to the presence of an ordering field which couples to the B2 order.Comment: To appear in Physical Review

Role of interfacial interactions on the anomalous swelling of polymer thin films in supercritical carbon dioxide

It has recently been shown that thin polymer films in the nanometer thickness range exhibit anomalous swelling maxima in supercritical CO 2 (Sc-Co 2 ) in the vicinity of the critical point of CO 2 . The adsorption isotherm of CO 2 on carbon black, silica surfaces, porous zeolites, and other surfaces, is known to exhibit anomalous maxima under similar CO 2 conditions. It is believed that because CO 2 possesses a low cohesive energy density, there would be an excess amount of CO 2 at the surfaces of these materials and hence the CO 2 /polymer interface. This might cause excess CO 2 in the polymer films near the free surface, and hence the swelling anomaly. In addition, an excess of CO 2 would reside at the polymer/substrate and polymer/CO 2 interfaces for entropic reasons. These interfacial effects, as have been suggested, should account for an overall excess of CO 2 in a thin polymer film compared to the bulk, and would be responsible for the anomalous swelling. In this study, we use in situ spectroscopic ellipsometry to investigate the role of interfaces on the anomalous swelling of polymer thin films of varying initial thicknesses, h 0 , exposed to Sc-CO 2 . We examined three homopolymers, poly(1,1′-dihydroperflurooctyl methacrylate) (PFOMA), polystyrene (PS), poly(ethylene oxide) (PEO), that exhibit very different interactions with Sc-CO 2 , and the diblock copolymer of PS- b -PFOMA. We show that the anomalous swelling cannot be solely explained by the excess adsorption of CO 2 at interfaces. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1313–1324, 2007Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/56015/1/21159_ftp.pd

Defining Chlorophyll-a Reference Conditions in European Lakes

The concept of “reference conditions” describes the benchmark against which current conditions are compared when assessing the status of water bodies. In this paper we focus on the establishment of reference conditions for European lakes according to a phytoplankton biomass indicator—the concentration of chlorophyll-a. A mostly spatial approach (selection of existing lakes with no or minor human impact) was used to set the reference conditions for chlorophyll-a values, supplemented by historical data, paleolimnological investigations and modelling. The work resulted in definition of reference conditions and the boundary between “high” and “good” status for 15 main lake types and five ecoregions of Europe: Alpine, Atlantic, Central/Baltic, Mediterranean, and Northern. Additionally, empirical models were developed for estimating site-specific reference chlorophyll-a concentrations from a set of potential predictor variables. The results were recently formulated into the EU legislation, marking the first attempt in international water policy to move from chemical quality standards to ecological quality targets

Intramolecular and Lattice Melting in n-Alkane Monolayers: An Analog of Melting in Lipid Bilayers

URL:http://link.aps.org/doi/10.1103/PhysRevLett.83.2362 DOI:10.1103/PhysRevLett.83.2362Molecular dynamics (MD) simulations and neutron diffraction experiments have been performed on n-dotriacontane ( n-C32D66) monolayers adsorbed on a graphite basal- plane surface. The diffraction experiments show little change in the crystalline monolayer structure up to a temperature of ~350K above which a large thermal expansion and decrease in coherence length occurs. The MD simulations provide evidence that this behavior is due to a phase transition in the monolayer in which intramolecular and translational order are lost simultaneously. This melting transition is qualitatively similar to the gel-to-fluid transition found in bilayer lipid membranes.Acknowledgment is made to the U.S. National Science Foundation under Grants No. DMR-9314235 and No. DMR-9802476, the Missouri University Research Reactor, and to the donors of The Petroleum Research Fund, administered by the ACS, for partial support of this research. We thank L. Criswell for assistance with the figures