Human serum albumin self-assembly on weak polyelectrolyte multilayer films structurally modified by pH changes

Adsorption of proteins onto film surfaces built up layer by layer from oppositely charged polyelectrolytes is a complex phenomenon, governed by electrostatic forces, hydrogen bonds, and hydrophobic interactions. The amounts of the interacting charges, however, both in polyelectrolytes and in proteins adsorbed on such films are a function of the pH of the solution. In addition, the number and the accessibility of free charges in proteins depend on the secondary structure of the protein. The subtle interplay of all these factors determines the adsorption of the proteins onto the polyelectrolyte film surfaces. We investigated the effect of these parameters for polyelectrolyte films built up from weak "protein-like" polyelectrolytes (i.e., polypeptides), poly(L-lysine) (PLL), and poly(glutamic acid) (PGA) and for the adsorption of human serum albumin (HSA) onto these films in the pH range 3.0-10.5. It was found that the buildup of the polyelectrolyte films is not a simple function of the pure charges of the individual polyelectrolytes, as estimated from their respective pKa values. The adsorption of HSA onto (PLL/PGA)n films depended strongly on the polyelectrolyte terminating the film. For PLL-terminated polyelectrolyte films, at low pH, repulsion, as expected, is limiting the adsorption of HSA (having net positive charge below pH 4.6) since PLL is also positively charged here. At high pH values, an unexpected HSA uptake was found on the PGA-ending films, even when both PGA and HSA were negatively charged. It is suggested that the higher surface rugosity and the decrease of the alpha-helix content at basic pH values (making accessible certain charged groups of the protein for interactions with the polyelectrolyte film) could explain this behavior.     

Rapid and reversible switching between superoleophobicity and superoleophilicity in response to counterion exchange

We use a simple layer-by-layer (LbL) assembly and counterion exchange technology to rapidly and reversibly manipulate the oleophobicity of the textured aluminum surfaces. Such textured surfaces can be produced by the HCl etching and boiling water treatment of the flat aluminum plates. The LbL deposition of polyelectrolytes is performed on these surfaces to generate the polyelectrolyte multilayer films. The films are able to coordinate with perfluorooctanoate anions, leading to the surfaces with different oleophobicity. The resulting surface produced by 1.5 cycles of polyelectrolyte deposition exhibits superoleophobicity by displaying contact angles greater than 150° with low surface tension liquids. Counterion exchange in this polyelectrolyte multilayer emerged easily to control the surface composition, which leads to tunable wettability that can be rapidly and reversibly switched between superoleophobicity and superoleophilicity.     

Molecularly smooth cellulose surfaces for adhesion studies

Cellulose is deposited on silicon wafer surfaces via spin coating from a solution of cellulose in dimethylacetamide (+7% lithium chloride). The resulting cellulose layers were analyzed by ellipsometry, AFM, FTIR, ICP-MS, X-ray reflectivity, and contact angle measurements. For cellulose concentrations below 0.07 wt% the wafer surfaces are covered with a network of cellulose fibrils. For concentrations between 0.07 and 0.5 wt%, closed films with thicknesses between 1.5 and approximately 10 nm are obtained. These films are molecularly smooth (rms roughness<2 nm). Higher concentrations result in thicker films with significantly rougher surfaces (rms roughness>2 nm). The cellulose layers were used to investigate cellulose/cellulose adhesion and their modification by polyelectrolytes. To this end the sticking behavior of cellulose beads was analyzed. It is demonstrated that the sticking of the beads depends on the type, amount, and adsorption symmetry of adsorbed polyelectrolyte. Low, incomplete polyelectrolyte coverage always enhances sticking, whereas for high coverage the symmetry of the polyelectrolyte coating is very important. In this case, sticking (adhesion) is enhanced if only one surface is covered with polyelectrolyte prior to contact. If both surfaces were fully covered with polyelectrolytes before contact, sticking (adhesion) is decreased.     

Phospholipid bilayers as biomembrane-like barriers in layer-by-layer polyelectrolyte films

Dipalmitoylphosphatidylcholine (DPPC) bilayer was created on the surface of an exponentially growing poly(glutamic acid)/poly(lysine) (PGA/PLL) layer-by-layer polyelectrolyte film. The lipid bilayer decreased the surface roughness of the polyelectrolyte film. The layer-by-layer construction of the polyelectrolyte film could be continued on the top of the DPPC layer. The lipid bilayer, however, formed a barrier in the interior of the polyelectrolyte film, which blocked the diffusion (a prerequisite for exponential growth) of the polyelectrolytes. Thus, a new growth regime started in the upper part of the polyelectrolyte film, which was added to embed the DPPC bilayer. The structure and the dynamics of the DPPC bilayer on the polyelectrolyte film surface remained similar to that of its hydrated multibilayers, except that the phase transition became wider. In the case of embedded DPPC bilayers, in addition, the phase-transition temperature also decreased. This is the result of interactions with the nonconcerted movements of the barrier-separated lower and higher parts of the polyelectrolyte film. Gramicidin A (GRA) as a model of lipid-soluble peptides and proteins was successfully incorporated into such DPPC films. The DPPC films, either with or without GRA, were remarkably stable; as many heating-cooling cycles to measure phase transition could be carried out without visible alterations as wanted.     

Stabilization of protein-loaded starch microgel by polyelectrolytes

The interaction of biocompatible polyelectrolytes (chargeable poly(amino acids)) with oxidized starch microgel particles has been studied. The aim was to form a polyelectrolyte complex layer around the outer shell of microgel particles filled with functional ingredients to slow down the release of the ingredients from the gel and make this process less sensitive to salt. First, the distribution of positively charged poly(l-lysine) (PLL) of two different molecular weights ("small", 15-30 kDa, and "large", 30-70 kDa) in the negatively charged gel particles was measured. The small PLL distributes homogeneously throughout the gel particles, but the large PLL forms a shell; i.e., its concentration at the outer layer of the particles was found to be much higher than in their core. This shell formation does not occur at a relatively high salt concentration (0.07 M). The large PLL was selected for further study. It was found that upon addition of PLL to lysozyme-loaded gel particles the protein is exchanged by PLL. The exchange rate increases with increasing pH, in line with the increasing electrostatic attraction between the gel and the polyelectrolyte. Therefore, it was decided to use also a negatively charged poly(amino acid), poly(L-glutamic acid) (PGA), to form together with PLL a stable polyelectrolyte complex shell around the gel particles. This approach turned out to be successful, and the PLL/PGA complex layer effectively slows down the release of lysozyme from the microgel particles at 0.05 M salt. In addition, it was found that the PLL/PGA layer protects the gel particle from degradation by α-amylase.     

Partial poly(glutamic acid) <--> poly(aspartic acid) exchange in layer-by-layer polyelectrolyte films. Structural alterations in the three-component architectures

Layer-by-layer (LBL) polyelectrolyte films were constructed from poly(L-glutamic acid) (PGA) and poly(L-aspartic acid) (PAA) as polyanions, and from poly(L-lysine) (PLL) as the polycation. The terminating layer of the films was always PLL. According to attenuated total reflection Fourier transform infrared measurements, the PGA/PLL and PAA/PLL films, despite their chemical similarity, had largely different secondary structures. Extended beta-sheets dominated the PGA/PLL films, while alpha-helices and intramolecular beta-sheets dominated the PAA/PLL films. The secondary structure of the polyelectrolyte film affected the adsorption of human serum albumin (HSA) as well. HSA preserved its native secondary structure on the PGA/PLL film, but it became largely deformed on PAA/PLL films. Both PGA and PAA were able to extrude to a certain extent the other polyanion from the films, but the structural consequences were different. Adding PAA to a (PGA/PLL)5-PGA film resulted in a simple exchange and incorporation: PGA/PLL and PAA/PLL complexes coexisted with their unaltered secondary structures in the mixed film. The incorporation of PGA into a (PAA/PLL)5-PAA film was up to 50% and caused additional beta-structure increase in the secondary structure of the film. The proportions of the two polyanions were roughly the same on the surfaces and in the interiors of the films, indicating practically free diffusion for both polyanions. The abundance of PAA/PLL and PGA/PLL domains on the film surfaces was monitored by the analysis of the amide I region of the infrared spectrum of a reporter molecule, HSA, adsorbed onto the three-component polyelectrolyte films.     

Molecular dynamics simulations of polyelectrolyte adsorption

We have performed molecular dynamics simulations of polyelectrolyte adsorption at oppositely charged surfaces from dilute polyelectrolyte solutions. In our simulations, polyelectrolytes were modeled by chains of charged Lennard-Jones particles with explicit counterions. We have studied the effects of the surface charge density, surface charge distribution, solvent quality for the polymer backbone, strength of the short-range interactions between polymers and substrates on the polymer surface coverage, and the thickness of the adsorbed layer. The polymer surface coverage monotonically increases with increasing surface charge density for almost all studied systems except for the system of hydrophilic polyelectrolytes adsorbing at hydrophilic surfaces. In this case the polymer surface coverage saturates at high surface charge densities. This is due to additional monomer-monomer repulsion between adsorbed polymer chains, which becomes important in dense polymeric layers. These interactions also preclude surface overcharging by hydrophilic polyelectrolytes at high surface charge densities. The thickness of the adsorbed layer shows monotonic dependence on the surface charge density for the systems of hydrophobic polyelectrolytes for both hydrophobic and hydrophilic surfaces. Thickness is a decreasing function of the surface charge density in the case of hydrophilic surfaces while it increases with the surface charge density for hydrophobic substrates. Qualitatively different behavior is observed for the thickness of the adsorbed layer of hydrophilic polyelectrolytes at hydrophilic surfaces. In this case, thickness first decreases with increasing surface charge density, then it begins to increase.     

Does the nanometre scale topography of titanium influence protein adsorption and cell proliferation?

To investigate the influence of titanium films with nanometre scale topography on protein adsorption and cell growth, three different model titanium films were utilized in the present study. The chemical compositions, surface topographies and wettability were investigated by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle measurement, respectively. The films share the same surface chemistry but exhibit different topographies on a nanometre scale. Thus, they act as model systems for biological studies regarding surface topography effects. The films were obtained by varying the deposition rate and the film thickness, respectively. These films displayed nanometre scale surface roughness (root mean square roughness, R_rms) from 2 to 21 nm over areas of 50 μm × 50 μm, with different grain sizes at their surfaces. Albumin and fibrinogen adsorption on these model titanium films were performed in this study. Bicinchoninic acid assay was employed to determine the amount of adsorbed protein on titanium film surfaces. No statistically significant differences, however, were observed for either albumin or fibrinogen adsorption between the different groups of titanium films. No statistically significant influence of surface roughness on osteoblast proliferation and cell viability was detected in the present study.     

Kinetics of the Formation of Nano-Sized Platinum Particles in Water-in-Oil Microemulsions

The association between low-charge-density polyelectrolytes adsorbed onto negatively charged surfaces (mica and silica) and an anionic surfactant, sodium dodecyl sulfate (SDS), has been investigated using surface force measurements, ellipsometry, and XPS. All three techniques show that the polyelectrolyte desorbs when the SDS concentration is high enough. The XPS study indicates that desorption starts at a SDS concentration of ca. 0.1 unit of cmc (8x10(-4) M) and that the desorption proceeds progressively as the SDS concentration is increased. Surface force measurements show that for the polyelectrolyte studied here, having 1% of the segments charged, the desorption proceeds without any swelling of the adsorbed layer. This behavior differs from that observed when polyelectrolytes of greater charge density are used. Copyright 2001 Academic Press.     

Normal and shear forces between a polyelectrolyte brush and a solid surface

The diblock copolymer poly(methyl methacrylate)‐b‐poly(sodium sulfonated glycidyl methacrylate) (PMMA‐b‐PSGMA) was end‐attached by its hydrophobic block (PMMA) onto mica hydrophobized by a stearic trimethylammonium iodide (STAI) layer, to form a polyelectrolyte brush immersed in water. With a surface force balance (SFB), we extended earlier measurements between two such brush layers for the case of normal and shear forces at different shear rates, surface separation, and compressions between one mica surface coated with STAI or a STAI‐diblock layer against a bare mica surface. After coating one of the surfaces with STAI, a long range attraction that results in a jump into an adhesive flat contact between the hydrophobic and hydrophilic surfaces was observed. A very different behavior was seen after forming the polyelectrolyte brush on the STAI‐coated surface. The long range attraction was replaced by repulsion, accompanied by very low friction during shear (ca. three orders of magnitude lower than with adsorbed polyelectrolytes). On further compression, a weak attraction to the adhesive contact was observed. From the final surface–surface contact separation, we deduce that most of the polyelectrolyte diblock brush layer was squeezed out from the gap, leaving the STAI layer and a small amount of the polymer attached to the surface. Stick‐sliding behavior was seen while applying shear, suggesting a dissipation mechanism caused by the trapped polyelectrolyte. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 193–204, 2005     

Wettability and surface composition of partly and fully regenerated cellulose thin films from trimethylsilyl cellulose

The wettability and surface free energy (SFE) of partly and fully regenerated cellulose model surfaces from spin coated trimethylsilyl cellulose were determined by static contact angle (SCA) measurements. In order to gain detailed insight into the desilylation reaction of the surfaces the results from SCA measurements were compared with data from other surface analytical methods, namely thickness measurements, X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance infrared spectroscopy (ATR-IR). Additionally, the influence of ultra high vacuum treatment (UHV) during XPS measurements on the water wettability and surface morphology of regenerated cellulose thin films was investigated. The wetting of polar and non-polar liquids increased with prolonged regeneration time, which is reflected in the higher SFE values and polarities of the films. After UHV treatment the water SCA of partly regenerated films decreases, whereas fully regenerated cellulose shows a higher water SCA. Therefore it is assumed that volatile desilylation products tend to adsorb on partly regenerated films, which strongly influences their wettability.     

Surface characterization of cotton coated by a thin film of polystyrene with and without a cross-linking agent

Thin polystyrene film coated on cotton was successfully formed by admicellar polymerization. Divinylbenzene (DVB) was used as a cross-linking agent to form networked polystyrene to improve film coverage. A wettability test and XPS analysis were used to characterize the coated surface. The optimum amount of DVB was around 1%. At this amount, the film coverage was most complete, as judged by the reduction of the O1s signal in XPS analysis.     

The Effect of Polymer Substrate Surface Basicity on the Adsorption of a Cationic Polyacrylamide

The adsorption of a cationic polyacrylamide onto polytetrafluoroethylene, bisphenol-A based epoxy resins, and acrylate substrates was characterized with X-ray photoelectron spectroscopy (XPS) and dynamic contact angle measurement in water. Surface acidity-basicity was quantified via dynamic contact angle measurement in water, ethylene glycol, and diiodomethane. The epoxy resins exhibited intermediate surface basicity and adsorbed the most polyelectrolyte, suggesting that specific substrate-adsorbate acid-base interactions govern adsorption of the cationic polyacrylamide onto surfaces of low to intermediate basicity. In general polar interactions appear to dominate the adsorption process. Advancing contact angle measurements have yielded quantitative fractional surface coverage information for polymer-on-polymer adsorption comparable to that obtained via XPS. Copyright 1999 Academic Press.     

Fabrication and characterization of plasma processed surfaces with tuned wettability

Engineered surfaces with controlled hydrophilic/ hydrophobic character have been fabricated by tailoring the substrate topography and chemistry. In this method, the substrate to be treated was first coated by a photoresist, which was then surface-roughened using SF6 plasma etching. The resulting rough texture was then transferred to the underlying silicon surface by over-etching of the photoresist. At this point, the topographically modified surface was modified chemically by controlled deposition of a thin polymer layer using plasma processing. In this way, both the surface texture and the surface chemistry could be varied independently, producing surfaces with variable wetting character, including super-hydrophilicity and super-hydrophobicity, depending on the choice of plasma polymer deposited. Chemical characterization demonstrates a correlation between the surface chemistry and the wettability of the samples after etching. The surface elementary composition contained more C-F groups as the measured contact angle increased, indicating that the change of wettability is due to both the roughness and the surface energy of the deposited photoresist. In the case of materials deposited on the plasma-treated rough surfaces, the strengthening of the wetting character is only due to the created surface roughness, as XPS analyses showed no significant chemical difference as compared to the flat polymer.     

纳米二氧化硅包覆颜料黄的研究

采用静电自组装技术成功地将纳米二氧化硅粒子包覆在颜料黄的表面.研究结果表明,预吸附的聚电解质层数显著影响纳米二氧化硅的吸附量.随着包覆二氧化硅层数的增加,覆盖率逐渐增加,但包覆三层二氧化硅后,覆盖趋于平衡.吸附的纳米二氧化硅不仅可以提高颜料黄的亲水性,而且还能够散射紫外线,尤其是波长小于270nm的紫外线,提高了颜料黄的耐候性,同时又不影响颜料黄本身的颜色.     

Effect of atmospheric-pressure plasma on adhesion characteristics of polyimide film

In this work, the effect of atmospheric-pressure plasma treatments on surface properties of polyimide film are investigated in terms of X-ray photoelectron spectroscopy (XPS), contact angles, and atomic force microscopy (AFM). The adhesion characteristics of the film are also studied in the peel strengths of polyimide/copper film. As experimental results, the polyimide surfaces treated by plasma lead to an increase of oxygen-containing functional groups or the polar component of the surface free energy, resulting in improving the adhesion characteristics of the polyimide/copper foil. Also, the roughness of the film surfaces, confirmed by AFM observation, is largely increased. These results can be explained by the fact that the atmospheric-pressure plasma treatment of polyimide surface yields several oxygen complexes in hydrophobic surfaces, which can play an important role in increasing the surface polarity, wettability, and the adhesion characteristics of the polyimide/copper system.     

Influence of bath temperatures on the wettability of copper films surface prepared by electroless plating method on beech wood

Copper films were coated on beech wood substrates by electroless plating method. The influence of bath temperature on the copper films properties was studied by varying the bath temperatures 25, 35, 45 and 55 °C. Scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS), X‐ray diffraction (XRD) pattern, X‐ray photoelectron spectroscopy (XPS), micro Raman spectroscopy and contact angle measurements were used to both characterize the physical and chemical copper films properties and understand the influence of bath temperature on the wettability of copper surface. In our studies, we have found that the gained copper mass significantly increased at 55 °C. The crystalline nature of the coated copper was confirmed by XRD. The presence of Cu₂O and CuO was observed by XPS and micro Raman techniques, which confirms the oxidization of the coated copper surface. Also these characterization techniques have shown the big influence of bath temperature on the morphology, grain size, chemical composition and the film thickness of the coated copper. The wettability was highly influenced by increasing CuO on the coated copper, which is increased by the bath temperature. The contact angle measurements have demonstrated the influence of C―O, O―C?O and CuO components of the surface on the wettability of the samples. Copyright © 2016 John Wiley & Sons, Ltd.     

Influence of nanoscale particle roughness on the stability of pickering emulsions

The wetting behavior of solid surfaces can be altered dramatically by introducing surface roughness on the nanometer scale. Some of nature's most fascinating wetting phenomena are associated with surface roughness; they have inspired both fundamental research and the adoption of surface roughness as a design parameter for man-made functional coatings. So far the attention has focused primarily on macroscopic surfaces, but one should expect the wetting properties of colloidal particles to be strongly affected by roughness, too. Particle wettability, in turn, is a key parameter for the adsorption of particles at liquid interfaces and for the industrially important use of particles as emulsion stabilizers; yet, the consequence of particle roughness for emulsion stability remains poorly understood. In order to investigate the matter systematically, we have developed a surface treatment, applicable to micrometer-sized particles and macroscopic surfaces alike, that produces surface coatings with finely tunable nanoscale roughness and identical surface chemistry. Coatings with different degrees of roughness were characterized with regard to their morphology, charging, and wetting properties, and the results were correlated with the stability of emulsions prepared with coated particles of different roughness. We find that the maximum capillary pressure, a metric of the emulsions' resistance to droplet coalescence, varies significantly and in a nonmonotonic fashion with particle roughness. Surface topography and contact angle hysteresis suggest that particle roughness benefits the stability of our emulsions as long as wetting occurs homogeneously (Wenzel regime), whereas the transition toward heterogeneous wetting (Cassie-Baxter regime) is associated with a loss of stability.     

Oscillatory forces of nanoparticle suspensions confined between rough surfaces modified with polyelectrolytes via the layer-by-layer technique

This paper addresses the systematic study of surface roughness effects on the internal structuring of silica nanoparticle suspensions under confinement. The confining surfaces are modified by physisorption of layers of oppositely charged polyelectrolytes with the so-called layer-by-layer technique. The layer-by-layer technique modifies the surface roughness without changing the surface potential of a multilayer with the same outermost layer, by increasing the number of constituent layers and ionic strength of the polyelectrolyte solutions and by selecting an appropriate pair of polyelectrolytes. The oscillatory forces of nanoparticle suspensions with a particle diameter of 26 nm are measured by a colloidal-probe atomic force microscope (CP-AFM). The characteristic lengths of the oscillatory force, i.e., wavelength, which indicates interparticle distance, and decay length, or particle correlation length, are not affected by the surface roughness. The corresponding reduction in the oscillatory amplitude and the shift in the phase correlate with an increase in surface roughness. Increasing surface roughness further induces a disappearance of the oscillations, and both confining surfaces contribute to the effect of surface roughness on the force reduction. In order to show an oscillatory force, the particles have to show positional correlation over a reasonably long range perpendicular to the surface, and the correlation function should be the same over a larger lateral area. This requires that both the particles and the surfaces have a high degree of order or symmetry; otherwise, the oscillation does not occur. A roughness of a few nanometers on a single surface, which corresponds to about 10% of the nanoparticle diameter, is sufficient to eliminate the oscillatory force.     

Internal structure of nanoporous TiO2/polyion thin films prepared by layer-by-layer deposition

The internal structure of porous TiO2 films prepared by electrostatic layer-by-layer deposition was investigated. The films were prepared by alternate dipping of solid substrates into dispersions of TiO2 nanoparticles and polycations, polyanions, or pure buffer solution, respectively. The surface charge of the amphoteric TiO2 particles was controlled by the pH of the aqueous dispersions. The morphology of the film surface was investigated by means of scanning electron microscopy. It was found that the surface roughness strongly depends on the polymeric material used for the deposition process but is independent of the ionic strength of the solution or the molecular weight of the polyions. The samples with rough surfaces feature strong light scattering. The porosity and internal structure of the TiO2/polyelectrolyte films were investigated by adsorption/desorption of dye molecules. A crude estimate yields an internal surface that is up to 160 times the plane surface of the substrate for a film thickness of 1 microm. The composition of the films was investigated by X-ray photoelectron spectroscopy (XPS). Detection of the XPS signal after each deposition step of the first three dipping cycles shows a significant increase of the relative surface coverage of Ti after the TiO2 deposition step and of PSS after the PSS deposition step. For later dipping cycles, such an increase was also detectable but less prominent.