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Typically, laterally patterned films are fabricated by lithographic techniques, external fields, or di-block copolymer self-assembly. We investigate the self-patterning of polyelectrolyte multilayers, poly(diallyldimethylammonium) (PDADMA)/poly(styrenesulfonate) (PSS)short. The low PSS molecular weight (Mw(PSSshort) = 10.7 kDa) is necessary because PSSshort is somewhat mobile within a PDADMA/PSSshort film, as demonstrated by the exponential growth regime at the beginning of the PDADMA/PSSshort multilayer build-up. No self-patterning was observed when the PDADMA/PSS film consisted of only immobile polyelectrolytes. Atomic force microscopy images show that self-patterning begins when the film consists of seven deposited PDADMA/PSSshort bilayers. When more bilayers are added, the surface ribbing evolved into bands, and circular domains were finally observed. The mean distance between the surface structures increased monotonously with the film thickness, from 70 to 250 nm. Scanning electron microscopy images showed that exposure to vacuum resulted in thinning of the film and an increase in the mean distance between domains. The effect is weaker for PSSshort-terminated films than for PDADMA-terminated films. The mechanism leading to domain formation during film build-up and the effect of post-preparation treatment are discussed.

Molecular surface gradients can constitute electric field landscapes and serve to control local cell adhesion and migration. Cellular responses to electric field landscapes may allow the discovery of routes to improve osseointegration of implants. Flat molecule aggregate landscapes of amine- or carboxyl-teminated dendrimers, amine-containing protein and polyelectrolytes were prepared on glass to provide lateral electric field gradients through their differing zeta potentials compared to the glass substrate. The local as well as the mesoscopic morphological responses of adhered osteoblasts (MG-63) with respect to the stripes were studied by means of Scanning Ion Conductance Microscopy (SICM) and Fluorescence Microscopy, in situ. A distinct spindle shape oriented parallel to the surface pattern as well as a preferential adhesion of the cells on the glass site have been observed at a stripe and spacing width of 20 μm. Excessive ruffling is observed at the spindle poles, where the cells extend. To explain this effect of material preference and electro-deformation, we put forward a retraction mechanism, a localized form of double-sided cathodic taxis.

Surface forces are used to investigate the polymer conformation and the surface charge of polyelectrolyte multilayers. Films are prepared from strong polyelectrolytes with low and high linear charge density at 0.1 M NaCl, namely poly(diallyldimethylammonium) (PDADMA) and poly(styrenesulfonate) (PSS). The multilayer has two growth regimes: in the beginning, the film can contain as many positive as negative monomers. After about 15 deposited layer pairs, a linear growth regime characterized by an excess of cationic PDADMA monomers occurs. Independent of the film composition, at preparation conditions, the film surface is flat, uncharged and partially hydrophobic. Surface force measurements at decreased ionic strength provide insight. For PSS-terminated films electrostatic forces are found. At the beginning of multilayer formation, the surface charge density is negative. However, in the linear growth regime it is positive and low (one charge per 200-400 nm

Lipid oxidation does strongly influence the self-organization of plasma membranes; the detailed influence is not yet clear. In this work, phospholipid monolayers at the air/water interface were used as model membranes. Oxidation was induced by the reactive oxygen species formed in a H2O2-enriched solution. The reaction was found to be diffusion-limited; the concentration of the reactive oxygen species was about 50 nMol. Isotherms were recorded for different phosphatidylcholines with saturated and unsaturated alkyl chains. For unsaturated lipids, the isotherms showed a constant relative molecular area increase after oxidization, independent of the molecular area and dependent on the degree of peroxidation. Similarly, the compressibility modulus was unchanged, but shifted to larger molecular areas. The correlation between peroxidation and changes of the interaction forces between the lipid molecules is discussed.

In the 1980s, Helmuth Möhwald studied lipid monolayers at the air/water interface to understand the thermodynamically characterized phases at the molecular level. In collaboration with Jens Als-Nielsen, X-ray reflectometry was used and further developed to determine the electron density profile perpendicular to the water surface. Using a slab model, parameters such as thickness and density of the individual molecular regions, as well as the roughness of the individual interfaces, were determined. Later, X-ray and neutron reflectometry helped to understand the coverage and conformation of anchored and adsorbed polymers. Nowadays, they resolve molecular properties in emerging topics such as liquid metals and ionic liquids. Much is still to be learned about buried interfaces (e.g., liquid/liquid interfaces). In this Article, a historical and theoretical background of X-ray reflectivity is given, recent developments of X-ray and neutron reflectometry for polymers at interfaces and thin layers are highlighted, and emerging research topics involving these techniques are emphasized.

Cardiolipin is a mitochondrial phospholipid with four alkyl chains and two phosphate moieties. Tetramyristoyl cardiolipin (TMCL, (14:0)4CL) monolayers at the air-water interface are characterized by compression isotherms, which show a liquid expanded/liquid condensed phase transition. The phase transition surface pressure πc depends on the composition of the aqueous solution. In a calculation, this is attributed to the electrostatic double layer, which is induced by the head groups of the model membrane, and competitive ion binding. The intrinsic binding constant is large for protons ( KH = 10 L/mol) and small for monovalent cations ( KM (Na+, K+, Cs+) = 10-3 L/mol). The different intrinsic binding constants explain the non-monotonic behavior of πc on increasing the salt concentration: raising the monovalent salt concentration increases πc by charging the TMCL monolayer until 0.1 mol/L, then screening effects dominate and decrease πc by reducing the electrostatic repulsion between lipid head groups. When at fixed 0.15 mol/L NaCl concentration, the concentration of divalent cations is increased, πc decreases. The intrinsic binding constants of divalent cations follow the sequence Sr2+ < Mg2+ < Mn2+ ≈ Zn2+ ≈ Ca2+ ( KD,Ca = 1.2 L/mol). The predictive power of the calculations was tested with different solutions.

Surface charges at the cell–biomaterial interface are known to determine cellular functions. Previous findings on cell signaling indicate that osteoblastic cells favor certain moderately positive surface charges, whereas highly positive charges are not tolerated. In this study, we aimed to gain deeper insights into the influence exerted by surface charges on the actin cytoskeleton and the cell shape. We analyzed surfaces with a negative, moderately positive, and highly positive zeta (ζ) potential: titanium (Ti), Ti with plasma polymerized allylamine (PPAAm), and Ti with a polydiallyldimethylammonium chloride (PDADMA) multilayer, respectively. We used the software FilaQuant for automatic actin filament quantification of osteoblastic MG-63s, analyzed the cell edge height with scanning ion conductance microscopy (SICM), and described the cellular shape via a mathematical vertex model. A significant enhancement of actin filament formation was achieved on moderately positive (+7 mV) compared with negative ζ-potentials (−87 mV). A hampered cell spreading was reflected in a diminished actin filament number and length on highly positively charged surfaces (+50 mV). Mathematical simulations suggested that in these cells, cortical tension forces dominate the cell–substrate adhesion forces. Our findings present new insights into the impact of surface charges on the overall cell shape and even intracellular structures.

International audience; Topographical and chemical features of biomaterial surfaces affect the cell physiology at the interface and are promising tools for the improvement of implants. The dominance of the surface topography on cell behavior is often accentuated. Striated surfaces induce an alignment of cells and their intracellular adhesion-mediated components. Recently, it could be demonstrated that a chemical modification via plasma polymerized allylamine was not only able to boost osteoblast cell adhesion and spreading but also override the cell alignment on stochastically machined titanium. In order to discern what kind of chemical surface modifications let the cell forget the underlying surface structure, we used an approach on geometric microgrooves produced by deep reactive ion etching (DRIE). In this study, we systematically investigated the surface modification by (i) methyl-, carboxyl-, and amino functionalization created via plasma polymerization processes, (ii) coating with the extracellular matrix protein collagen-I or immobilization of the integrin adhesion peptide sequence Arg-Gly-Asp (RGD), and (iii) treatment with an atmospheric pressure plasma jet operating with argon/oxygen gas (Ar/O-2). Interestingly, only the amino functionalization, which presented positive charges at the surface, was able to chemically disguise the microgrooves and therefore to interrupt the microtopography induced contact guidance of the osteoblastic cells MG-63. However, the RGD peptide coating revealed enhanced cell spreading as well, with fine, actin-containing protrusions. The Ar/O-2-functionalization demonstrated the best topography handling, e.g. cells closely attached even to features such as the sidewalls of the groove steps. In the end, the amino functionalization is unique in abrogating the cell contact guidance

Polystyrene sulfonate (PSS) of different molecular weight M(w) is adsorbed to oppositely charged DODAB monolayers from dilute solutions (0.01 mmol/L). PSS adsorbs flatly in a lamellar manner, as is shown by X-ray reflectivity and grazing incidence diffraction (exception: PSS with M(w) below 7 kDa adsorbs flatly disordered to the liquid expanded phase). The surface coverage and the separation of the PSS chains are independent of PSS M(w). On monolayer compression, the surface charge density increases by a factor of 2, and the separation of the PSS chains decreases by the same factor. Isotherms show that on increase of PSS M(w) the transition pressure of the LE/LC (liquid expanded/liquid condensed) phase transition decreases. When the contour length exceeds the persistence length (21 nm), the transition pressure is low and constant. For low-M(w) PSS (7 kDa) the LE/LC transition of the lipids and the disordered/ordered transition of adsorbed PSS occur simultaneously, leading to a maximum in the contour length dependence of the transition enthalpy. These findings show that lipid monolayers at the air/water interface are a suitable model substrate with adjustable surface charge density to study the equilibrium conformation of adsorbed polyelectrolytes as well as their interactions with a model membrane.

Gold surfaces with a strongly preferential Au{100} orientation were prepared by annealing of commercial gold foil in an oven at temperatures between 400 and 900 °C. The annealing also led to an improved crystallinity and growth of grain size. A similar surface restructuring was observed upon ultrasonication of the gold foil at room temperature in a water bath.

Aluminum phosphate was deposited onto bundles of carbon fibers and flat glassy carbon substrates using atomic layer deposition by exposing them to alternating pulses of trimethylaluminum and triethylphosphate vapors. Energy dispersive X-ray spectroscopy (EDXS) and solid state nuclear magnetic resonance (SS-NMR) spectra confirmed that the coating comprises aluminum phosphate (orthophosphate as well as other stoichiometries). Scanning electron microscopic (SEM) images revealed that the coatings are uniform and conformal. After coating, the fibers are still separated from each other like the uncoated fibers. Thermogravimetric analysis (TGA) indicates an improvement of oxidation resistance of the coated fibers compared to uncoated fibers.

A crucial factor for ingrowth of permanent implants in the bone is the rapid cellular acceptance. The topographical features often follow mechanical aspects for implant stability. But several of these implants fail due to insufficient cell adhesion. Cells are able to perceive the physicochemical properties of their surrounding and to pass these signals into the cell to modulatetheir adhesion structures, growth or production of extracellular matrix. However, the complex cell physiology at the material interface is not yet fully understood, particular on stochastically structured topographies resulting from industrial production. We could find out that corundum blasted titanium hampered the organization of actin filaments inside the cells, clustered adhesion components, e. g. beta-1 integrins and tensin, and the cells bridged the valleys which reduces cellsubstrate contacts. These morphological changes strongly diminished the mineralization of osteoblasts. To shed light on cause and effect we reduced the physical complexity of the material surface by introduction of regular micro-structures (pillars, grooves) using deep reactive ion etching. Now it was more obvious what cells are doing on sharp edged topographies - the actin filaments of our cells were clustered around the pillars. As a result the intracellular calcium signaling and the protein synthesis were impaired. Our recent findings indicated an attempted phagocytosis of the micro-pillars by osteoblasts. Therefore we conclude that implants used in orthopedic surgery should avoid any sharp-edged topographical features that could induce phagocytosis by the surrounding cells, which is an unnecessarily energy consuming process. © 2017 Trans Tech Publications, Switzerland.

Giant unilamellar liposomes of the synthetic cardiolipin 1′,3′-bis[1,2-dimyristoyl-sn-glycero-3-phospho]-sn-glycerol give chronoamperometric current peaks at a stationary mercury electrode. The signals are due to the adhesion and spreading of the liposomes on the hydrophobic mercury surface. The potential dependence shows a minimum of the peak frequency at the point of zero charge, a large maximum of peak frequency at about −0.2 V and a second, however, smaller maximum at −0.8 V. The electrochemical behaviour of the liposomes indicates phase transitions of the cardiolipin which could be also observed in differential scanning calorimetry.

Silver nanoparticles (4.5 nm average radius) are used as the first negatively charged layer of a polyelectrolyte multilayer prepared subsequently from poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate) (PSS) solutions with 1 M KCl. After adsorption of a PAH layer on top of the silver nanoparticle monolayer, particle aggregation occurs, as evidenced by the double peak of the UV-vis absorption spectrum and by the decreased number of the objects found with AFM. On adsorption of the first PSS layer on top of the Ag/PAH sandwich, the nanoparticles remain close as is indicated by a the reduced object count and the changed absorption spectrum. If the PAH layer covering the Ag nanoparticles is adsorbed from salt-free solution, the nanoparticles remain isolated. Apparently, the aggregation is mediated by the PAH adsorbing in coiled conformation. Additionally, UV-vis and X-ray reflectivity evidence is found for lateral yet not vertical nanoparticle movement when polyelectrolytes adsorb, even if the adsorbing coils do not touch the nanoparticles directly.

The behaviour of hydrogen in metals has attracted scientific attention for many decades and is interesting from both basic research and technological points of view. Metal hydrides find a wide range of applications of which the most prominent is the reversible hydrogen storage. This is of great importance in view of possible future hydrogen economy. Moreover the high diffusivity of hydrogen also makes nanoscaled Me-H systems interesting possibilities for sensor applications, and surface reactions with hydrogen on Pt, Pd, Ni, and other metals are applied in catalysis, particularly in fuel cells.

nm thick Nickel films were treated in a microwave plasma (SLAN, 2.45 GHz) with Argon as working gas. Oxygen and hydrogen containing plasma were subsequently applied to achieve oxidation and reduction of the metallic nickel. The plasma-treated samples were investigated by complementary techniques: grazing incidence x-ray diffractometry (GIXD), x-ray reflectometry (XR) and atomic force microscopy (AFM). The combination of these techniques allows a detailed analysis of the occurring plasma-chemical processes. Oxygen plasma treatment results in the formation of NiO on the metallic Ni grains. The domain size of the formed NiO is appreciable smaller than that of the Ni domains. The kinetics of the oxidation process can be described using the "shrinking core" model. The oxide formation rate depends on the sample history, i.e. on the number of oxida- tion/reduction cycles carried out. The first oxidation process is controlled by oxygen diffu- sion into the film, the kinetics of the subsequent oxidation cycles is more reaction controlled. Hydrogen plasma treatment causes a fast reduction up to the level of metallic Ni.

Ultrathin gallium oxide layers with a thickness of 2.8 ± 0.2 nm were transferred from the surface of liquid gallium onto solid substrates, including conjugated polymer poly(3-hexylthiophene) (P3HT). The gallium oxide exhibits high mechanical stability, withstanding normal pressures of up to 1 GPa in contact mode scanning force microscopy imaging. Moreover, it lowers the rate of photodegradation of P3HT by 4 orders of magnitude, as compared to uncovered P3HT. This allows us to estimate the upper limits for oxygen and water vapor transmission rates of 0.08 cm(3) m(-2) day(-1) and 0.06 mg m(-2) day(-1), respectively. Hence, similar to other highly functional coatings such as graphene, ultrathin gallium oxide layers can be regarded as promising candidates for protective layers in flexible organic (opto-)electronics and photovoltaics because they offer permeation barrier functionalities in conjunction with high optical transparency.

Langmuir monolayers of polymacromonomers (cylindrical brushes) with poly(vinyl)pyridine side chains of different length, polyPV P20.8 and polyPV P46.7, are studied at the air?water interface by means of x-ray diffraction and reflectivity. The advantages of measurements on an aqueous subphase, which contains NaI, are demonstrated. This subphase does not affect the structure of an uncharged monolayer, although NaI is incorporated into the side chains, it provides an enhanced contrast for the x-ray investigations. A structural transition from aligned single molecules to a homogeneous monolayer is found, which is attributed to intra-?and intermolecular interactions.

PEE212-PEO112 diblock copolymer monolayers are studied at the air/water interface. At large molecular areas, with X-ray reflectivity, PEE domains are observed, which are partly immersed into the water. The domain thickness increases on compression (28 to 40 A). With off-specular X-ray reflectivity, an average domain radius of 750 A is found, but there are also smaller domains. Due to these space constraints, most PEO blocks form a brush beneath the PEE domains. Only a few PEO blocks form a corona surrounding the domains and adsorb flatly onto the air/water interface. The PEO desorption transition is observed at the typical pressure of 9 mN/m, when the flatly adsorbed PEO is compressed at a domain fraction of 95%. It occurs at 6 A2/EO monomer, about half the value found for lipopolymers or diblock copolymers with NPEE approximately NPEO or NPEENPEO. Apparently, the thickness of the PEE domains is determined by the forces from the two interfaces, not by the PEO block, for which flat adsorption beneath the domain would be more favorable instead of formation of a PEO brush.

Experiments were carried out on a water-based ferrofluid (gamma-Fe2O3 with carboxydextran shell) using photon correlation spectroscopy (PCS), atomic force microscopy, and magnetic nanoparticle relaxation measurements. The experiments were designed with the aim to relate the Néel signals that are in theory generated by large single core particles with nanoscopic properties, that is, particle size, particle size distribution, shell properties, and aggregation. For this purpose, the ferrofluid was fractionated by magnetic fractionation and size exclusion chromatography. Nanoparticles adsorbed onto positively charged substrates form a two-dimensional monolayer. Their mean core diameters are in the range of 6 to about 20 nm, and particles above 10 nm are mostly aggregates. The hydrodynamic particle diameters are between 13 and 80 nm. The core diameter of the smallest fraction is confirmed by X-ray reflectometry; the surface coverage is controlled by bulk diffusion. Comparison with the hydrodynamic radius yields a shell thickness of 3.8 nm. Considering the shell thickness to be constant for all particles, it was possible to calculate the apparent particle diameter in the original ferrofluid from the PCS signals of all fractions. As expected, the small cores yielded no Néel relaxation signals in freeze-dried samples; however, the fractions containing mostly aggregates yielded Néel relaxation signals.

Amphiphilic block copolymers consisting of a fluid hydrophobic (poly(ethyl ethylene), PEE) and a hydrophilic (poly(ethylene oxide), PEO) block form monolayers at the air/water interface. With X-ray and neutron reflectivity, the density profile of PEE432−PEO484 was investigated. It was found that the polymer adsorption layer consists of a homogeneous PEE and a solubilized PEO block, which can be laterally compressed by a factor of 3. The PEE thickness increases in inverse proportion to the molecular area, and the PEO brush follows the scaling law predicted for a brush in a good solvent. However, the stretching of the two blocks roughens the PEE−PEO interface, causing a transition from a PEO monolayer adsorbed to a hydrophobic interface (0.8−1.1 nm thick) to a PEE−PEO/water interfacial layer of 3 nm thickness. This transition of the interfacial layer highlights the rich phase behavior of amphiphilic block copolymers, which resembles that of lipids and nonionic surfactants.

Polyelectrolyte adsorption onto an oppositely charged interface is determined by electrostatic and secondary interactions. Since polyelectrolytes precipitate at elevated temperatures, the secondary interactions are presumably temperature dependent. This idea is tested for poly(allylamine) hydrochloride/polystyrene sulfonate (PAH/PSS) films adsorbed from aqueous KCl solution (high salt conditions) at temperatures between 5 and 40 °C. KCl was chosen because the films were thicker than those obtained from NaCl or CsCl solutions indicating strong specific binding between K and PSS. The film thickness increases continuously with the adsorption temperature; the changes amount to 20−40%, depending on salt conditions. Furthermore, the roughness is increased, up to a factor of 5. The latter is attributed to the decreased percentage of strong electrostatic bonds within the polyelectrolyte multilayer. Another path to increased roughening is using low-weight polymers with a contour length similar to the thickness of ...

The method of X-ray reflectometry with electron density “labeling” of polyampholytes by heavy counterions has been demonstrated for measuring the adsorption profiles of gelatin at both hydrophobic ...

Colloidal gold adsorbed onto positively charged substrates forms a two-dimensional layer with a maximum coverage of 1 colloid/1000 nm2 as shown by optical absorption spectroscopy, small-angle X-ray scattering, and atomic force microscopy. Positively charged substrates are obtained by either chemisorption of end-group-functionalized silanes or by polycation adsorption. Bulk diffusion controls the gold adsorption; thus lower coverages can also be achieved. The optical spectra not only contain information on single colloids but also on their mutual interactions, as well as on the polymeric and solvent environments. Absorption spectra based on Mie and Maxwell−Garnett theory are calculated. The films remain stable on exchange of the external solvent. The local dielectric environment is shown to not only influence the position of the absorption band but also, more drastically, the intensity (by a factor of 2.5), in agreement with theoretical predictions (±15%). Particle aggregation induced by branched polycatio...

Monolayers of a statistical copolymer with a poly(methacrylate) chain and hydrophilic and hydrophobic side groups are investigated at the air/water interface. The isotherms suggest a fluid and a frozen phase. With in-situ X-ray reflectivity the monolayer thickness is determined to be 2.5 nm or less. The shear viscosity in the fluid phase is extremely high yet can be described in the framework of the free area model. However, the parameter which characterizes the overlap of holes available for a diffusing monomer unit is a factor of 2 higher than expected, suggesting local diffusion barriers formed by nanosized clusters. In the glassy phase single-molecule fluorescence shows anomalous diffusion in an ≈140 nm cage (cf. ref 1), indicating that the clusters touch. The aggregates are mainly formed by the hydrophilic monomers, as both the X-ray data and the isotherms suggest.

We present a computer-controlled technique to measure the distance-dependent forces in the surface forces apparatus. The power of our setup is shown by a measurement of the repulsive forces between mica surfaces immersed in a 0.01 M NaCl solution. At close distances we find an oscillatory force with a periodicity of 0.30 nm, which roughly corresponds to the diameter of a water molecule. For the distance determination we use the standard interferometric technique: the interferometer consists of a medium sandwiched between two mica sheets of equal thickness silvered on the backside. The surface separation is measured by comparing the resonance wavelength to the one obtained from contacting mica sheets. By substitution of the eye by a CCD-camera we improve the reproducibility of the method and we can determine the cavity parameters quantitatively.

Monolayers of the phospholipids 1,2-dipalmitoylphosphatidylethanolamine (DPPE) and 1,2-dipalmitoylphosphatidylcholine (DPPC) are studied at the water/air interface in contact with n-hexadecane, n-dodecane, and bicyclohexyl by null ellipsometry and X-ray reflectivity along the isotherms. From recent diffraction data we derive refractive indices nx and nz to calculate the thickness of the mixed films in the condensed phase by ellipsometry. The thickness is compared with the results from X-ray reflectivity measurements. Both methods reveal that the mixed lipid/hydrocarbon film is not covered by a thin hydrocarbon film as known from short chain alcanes like hexane. The incorporation of the hydrocarbon affects the film thickness by reducing the tilt angle of the lipids. This way DPPC, which due to the large head group does not exhibit a non tilted condensed phase at the water/air interface at all, enlarges its value for nz at the expense of nx, yielding a condensed mixed phase with zero tilt angle. The resulti...

It is shown that a monolayer of random poly(methacrylate) copolymer with a hydrophobic and a hydrophilic substituent exhibits a transition from the fluid to amorphous state. Above this transition any amphiphilic molecules mixed with the monolayer are immobile. Furthermore, such functionalized lipids are immobilized in the monolayer during the Langmuir-Blodgett transfer. The hydrophilic head-groups of the biotin-lipids remain on the formerly water-adjacent side of the monolayer, even if this side is exposed to air

Because of its outstanding ability to image and manipulate single molecules, atomic force microscopy (AFM) established itself as a fundamental technique in nanobiotechnology. (1) We present a new modality that distinguishes single nanoparticles by the surrounding magnetic field gradient. Diamagnetic gold and superparamagnetic iron oxide nanoparticles become discernible under ambient conditions. Images of proteins, magnetolabeled with nanoparticles, demonstrate the first steps toward a magnetic analogue to fluorescence microscopy, which combines nanoscale lateral resolution of AFM with unambiguous detection of magnetic markers.

For the first time, the formation and growth of a molecular superstructure within a lipopolymeric monolayer on the water surface is directly observed by small-angle grazing incidence diffraction. Nanoscopic stripes of ordered alkyl chains and solubilized polymer alternate.1 At the onset of the superstructure formation, the smallest stripe periodicity is measured. Then, the periodicity relaxes (up to 170 A), even if the monolayer is further compressed. This threshold behavior is attributed to a very high local pressure necessary for stripe alignment. On solid substrates, the superstructure periodicity is decreased down to 120 A because of dehydration of the polymer moieties.

Polystyrene sulfonate (PSS 77 kDa) adsorbed onto oppositely charged dioctadecyldimethylammonium bromide (DODA) monolayers at the air/water interface is investigated with X-ray reflectivity and grazing incidence diffraction. The alkyl tails of DODA in the condensed phase form an oblique lattice with large tilts and intermediate azimuth angle. On PSS adsorption, the alkyl tail structure is maintained; only the tilt angle changes. Bragg peaks caused by flatly adsorbed, aligned PSS chains are observed, when DODA is in the fluid and also when it is in the condensed phase. The two-dimensional lamellar phase is only found at intermediate PSS bulk concentrations (0.001 - 1 mmol/L). In this phase, the PSS coverage can be varied by a factor of 3, depending on DODA molecular area and polymer bulk concentration. Charge compensation in the lamellar phase is almost achieved at 1 mmol/L. At larger bulk concentrations, PSS adsorbs flatly yet without chain alignment. Presumably, a necessary condition for a two-dimensional lamellar phase is a pronounced electrostatic force which causes a large persistence length as well as repulsion between the aligned chains.

A shift in plasmon surface resonance is measured for colloidal solutions of gold nanoparticles upon adsorption of polyampholyte (gelatin). It is demonstrated that the shift in wavelength of the absorption maximum can quantitatively yield measurements of the adsorbed amount as well as information about the structure of the adsorbed polymer layer. Semiquantitative agreement is found with calculations based on the Mie theory in the quasi-static limit. The method is demonstrated to provide quantitative measurements of the kinetics of biopolymer adsorption onto colloidal nanoparticles in solution.

A recently introduced method for the characterization of magnetic nanoparticles (MNPs) based on the analysis of the temperature-dependent Neel relaxation signal (TMRX) has been applied to characterize maghemite particles with different particle size distributions. The samples were made using an improved magnetic fractionation method for a ferrofluid with a broad particle size distribution. The temperature range of the measurement set-up has been extended from 315 K down to 4 K to detect even the smallest particles in the fractions. A mean magnetically relevant particle size has been derived from TMRX and low temperature coercivity measurements and has been compared to the physical size determined by atomic force microscopy (AFM) investigations.

The consecutive layer-by-layer adsorption of poly(allylamine hydrochloride) (PAH) and poly(styrenesulfonate) (PSS) on colloidal charged latex particles is investigated by measuring the electrophoretic mobility as a function of pH and ionic strength over a broad range (electrophoretic fingerprinting). Meaningful interpretation of the data required the development of a nonlinear approach to hairy particle electrophoresis including dissociation, adsorption, and association. Steric and electrostatic exclusion of mobile ions from the hairy layer has been considered. Also, the surface conductivity correction is extended to the case of charged hairy layer particles. We deposited up to three polyelectrolyte layers. The following were found: (i) Each layer deposition is accompanied by charge overcompensation and (ii) Not only the top layer but also the underneath layers and the naked latex particle surface contribute to the particle mobility. This can be interpreted as an incomplete coverage or a polyelectrolyte ...