The influence of electrostatic forces on protein adsorption

In this paper we investigate the importance of electrostatic double layer forces on the adsorption of human serum albumin by UV-ozone modified polystyrene. Electrostatic forces were measured between oxidized polystyrene surfaces and gold-coated atomic force microscope (AFM) probes in phosphate buffered saline (PBS) solutions. The variation in surface potential with surface oxygen concentration was measured. The observed force characteristics were found to agree with the theory of electrical double layer interaction under the assumption of constant potential. Chemically patterned polystyrene surfaces with adjacent 5 microm x 5 microm polar and non-polar domains have been studied by AFM before and after human serum albumin adsorption. A topographically flat surface is observed before protein adsorption indicating that the patterning process does not physically modify the surface. Friction force imaging clearly reveals the oxidation pattern with the polar domains being characterised by a higher relative friction compared to the non-polar, untreated domains. Far-field force imaging was performed on the patterned surface using the interleave AFM mode to produce two-dimensional plots of the distribution of electrostatic double-layer forces formed when the patterned polystyrene surfaces is immersed in PBS. Imaging of protein layers adsorbed onto the chemically patterned surfaces indicates that the electrostatic double-layer force was a significant driving force in the interaction of protein with the surface.     

DPD Molecular Simulations of Asphaltene Adsorption on Hydrophilic Substrates: Effects of Polar Groups and Solubility

Adsorption of asphaltenes onto a polar substrate (e.g., a mineral) was modeled with dissipative particle dynamics (DPD) simulations, using continental asphaltene models. The adsorption mechanisms in 10–20% wt, of asphaltene in toluene/ heptane solutions were studied (well above the solubility limit). The structure in the adsorbed layer was highly sensitive to the presence of polar groups in the alkyl side chains and heteroatom content in the aromatic ring structure. Four types of asphaltene models were used: completely apolar (zero adsorption), apolar chains and polar heteroatoms, polar chains and no heteroatoms, and polar chains and heteroatoms (maximum adsorption). One hundred asphaltene monomers were distributed homogeneously in the solvent initially, in a ～(10 nm)³ domain.

Asphaltene monomers adsorbed irreversibly on the substrate via the polar group in the side chains, resulting in an average perpendicular orientation of the aromatic rings relative to the substrate. More frequent π–π stacking of the aromatic rings occurred for less solubility (more heptane), as in aggregates. With apolar side chains, only the heteroatoms in the aromatic ring structure had affinity to the substrate, but the ring plane did not have any preferred direction.

An important finding is that the aromatic ring assemblies “shielded” the substrate and polar groups that were anchored to the substrate, resulting in an effective non-polar surface layer seen by asphaltenes in the bulk, leading to much lower adsorption probability of the remaining asphaltenes. This “adsorption termination” effect leads to mono-layer formation. Continued adsorption with multilayering and reversible nanoaggregate adsorption occurred when both side chains in the model asphaltene (located on opposite sides of the aromatic sheet) contained polar groups, with a higher probability of exposing further polar groups to the bulk asphaltene. The general conclusion is that the number and position of the polar groups in side chains determine to a large degree the adsorption and aggregation behavior/efficiency of (continental) asphaltenes, in line with experimental evidence. The heteroatoms in the aromatic ring structure plays a more passive role in this context, only by providing organization via more π–π stacking in the adsorbed layer, and in aggregates.     

The influence of the adsorbent amount on the changes in molecular mass distribution of polymers under adsorption from mixtures

Changes in the molecular mass distribution (MMD) for polymer as a result of adsorption from binary and ternary solutions have been studied by the exclusion chromatography method. It was found that the affinity of polymer components to a surface has a crucial influence on the changes in MMD of polymers. The diminution of polydispersity in solutions after adsorption was observed for two polymers. In the case of the polar polymer poly(butyl methacrylate) (PBMA) the diminution of polydispersity is caused mainly by the preferential adsorption of low-molecular-mass fractions, whereas in the case of the nonpolar polymer polystyrene (PS) it is caused by the transition of the high-molecular-mass fractions onto the adsorbent surface. The analysis of experimental results indicates that the quantity of the adsorbent affects the composition of the adsorption layer formed by polymers of different chemical nature.     

十二烷基苯磺酸钠在SiO2表面聚集的分子动力学模拟

采用分子动力学方法研究了阴离子表面活性剂十二烷基苯磺酸钠(SDBS)在无定形SiO2固体表面的吸附. 设置不同的水层厚度, 观察固液界面和气液界面吸附的差异. 模拟发现表面活性剂分子能够在短时间内吸附到SiO2表面, 受碳链和固体表面之间相互作用的影响形成表面活性剂分子层, 并依据吸附量的大小形成不同的聚集结构; 在水层足够厚的情况下, 由于有较多的表面活性剂分子吸附在固体表面,从而形成带有疏水核心的半胶束结构; 计算得到的成对势表明极性头与钠离子或水分子之间的结合或解离与二者之间的能垒有关, 解离能垒远大于结合能垒, 引起更多Na+聚集在极性头周围而只有少数Na+存在于溶液中; 无论气液还是固液界面, 极性头均伸向水相, 与水分子形成不同类型的氢键. 模拟表明, 分子动力学方法可以作为实验的一种补充, 为实验提供必要的微观结构信息.     

Assessment of the Surface Heterogeneity of Talc Materials

The hydrophobic and hydrophilic components of the surface of talc materials in aqueous solution were determined using ionic surfactants and their polar headgroup adsorption isotherms. The hydrophilic and hydrophobic surface areas are inferred from the amount of probe molecule adsorbed and the structure of the adsorbed layer. Natural dispersion of talc shows at 298 K a pH of 9.4 and the electrophoretic measurements indicate that the particles are negatively charged. The hydrophilic surface area is estimated from the adsorption of benzyltrimethylammonium ions (BTMA(+)) through electrostatic interactions as supported by the increase of divalent ions in the bulk phase and the decrease in the exothermic displacement enthalpy. It was also observed from the adsorption isotherm of benzene sulfonate anions that the density of positive surface sites is very low and is thus neglected. The adsorption of an anionic surfactant essentially occurs through dispersive interactions between the nonpolar organic tail of the molecule and the hydrophobic surface. Furthermore, some assumptions on the structure of dodecyl sulfate surfactant aggregates at the interface allow the hydrophobic part of the talc particles to be estimated. The cationic surfactant adsorption has been investigated and found to corroborate the hydrophilic and hydrophobic area values first obtained. Copyright 2001 Academic Press.     

Comparative simulation study of nitrogen and ammonia adsorption on graphitized and nongraphitized carbon blacks

Grand canonical Monte Carlo simulation is used to study the adsorption of nitrogen at 77 K and ammonia at 240 K to represent weakly polar and polar molecules, respectively, on infinite and finite graphite surfaces. These graphite surfaces were modeled with different percentages of carbons removed (defects) from the top graphite layer. Increasing the number of defects increases the adsorption and the isosteric heat of nitrogen at low pressure. At moderate pressures the amount adsorbed is less due to the disruption in the packing of the nitrogen in the first layer. In contrast, the adsorption of ammonia at all pressures is reduced as the percentage of defects is increased. This is due to the disruption in ammonia bonding caused by the defects. The condensation-like step change in the ammonia isotherm on the perfect graphite surface is not observed for any of these surfaces with defects even for the case of only 10% defects. At high percentage of defects the adsorption isotherm is close to Henry law behavior for much of the pressure range. The adsorption on finite surfaces shows that the amount adsorbed for both molecules decreases compared with that of the infinite surfaces, resulting from interaction potentials with the surface and other fluid molecules at the edge. The decrease is much greater for the ammonia adsorption because the bonding between ammonia molecules is disrupted, meaning that the adsorption cannot follow the mechanism of condensation seen for the infinite surface.     

Using ferroelectric poling to change adsorption on oxide surfaces

Adsorption has been invoked to explain many phenomena in ferroelectric materials including the unanticipated stability of ultrathin ferroelectric films; however, the intrinsic surface properties of ferroelectric oxides have been largely unexplored. Therefore, the effect of ferroelectric poling on the adsorption/desorption of two polar molecules, acetic acid and 2-propanol, and one nonpolar molecule, dodecane, on LiNbO3(0001) was compared. The two polar molecules were found to adsorb significantly more strongly on the positive surface. Temperature-programmed desorption (TPD) data yielded desorption pre-exponentials of the two polar molecules more than 11 orders of magnitude lower than expected. Ferroelectric materials are also intrinsically pyroelectric, and it is shown that the unusually low desorption pre-exponentials can be explained by temperature dependent heats of adsorption that result from changes in the surface dipole as the samples are heated. This conclusion was supported by dodecane adsorption/desorption, which was independent of polarity with normal desorption pre-exponentials. The differences between the polar and nonpolar molecules indicate that interactions between polar molecules and ferroelectric surfaces are dominated by electrostatics. It is shown that adsorption energy differences between positive and negative surfaces are large enough to switch the polarity of ferroelectric thin films.     

A study of sodium bis(2-ethylhexyl) sulfosuccinate adsorption on silica from silver and gold organosols

Adsorption of sodium bis(2-ethylhexyl) sulfosuccinate (Aerosol OT) and silver and gold nanoparticles on SiO₂ from heptane solutions has been investigated by spectophotometery and CHN analysis. The adsorption isotherm of Aerosol OT is described by the Langmuir equation. Sorption capacity (2.4 × 10^–4 mol/g), sorption constant (9.0 m³/mol), and area per Aerosol OT molecule in an adsorption layer (0.83 nm²) have been determined. It has been shown that, at Aerosol OT concentrations lower than 6 × 10^–4 M, gold and silver ((0.3–6) × 10^–4 M) are simultaneously extracted by 98%; however, they have no effect on the adsorption and determination of the surfactant.     

反气相色谱法测定锌镁铝类水滑石的表面性能

采用水热合成法制备了锌镁铝类水滑石(ZnMgAl-HTLC),利用X射线衍射仪(XRD)对ZnMgAl-HTLC的晶体结构进行了表征,并以一系列非极性和极性分子为探针分子,采用反气相色谱法(IGC)研究了ZnMgAl-HTLC的表面性能.结果表明:XRD特征衍射峰窄、尖、高,水热合成法能够制得纯度较高的ZnMgAl-HTLC; ZnMgAl-HTLC表面吸附自由能小于零,表面色散自由能最大为6.02 mJ/m²,酸碱作用自由能最大为5.33 kJ/mol,吸附焓为43.6 kJ/mol,吸附熵为0.15 kJ/mol.本文的反气相色谱方法对研究锌镁铝类水滑石的表面性能具有重要的指导意义.     

Application of programmed thermodesorption of the liquid under quasi-isothermal conditions to investigate physicochemical properties of liquid layers and solid surfaces

This paper presents the results of measurements of the programmed thermodesorption of polar and nonpolar liquids from the surface of different types of solids. The course of thermodesoption was found to depend on the properties of the solid and the wetting liquid. Thermodesorption occurred not exponentially but in steps, which reflects the noncontinuous changes in the properties of the surface layer with the distance from the solid surface. This effect intensified with the increase in polarity of the wetting liquid and the heterogeneity of the solid surface. The earlier investigations showed that application of the method of differential thermal analysis allowed determination of the distribution of the adsorption potential of the liquid on the solid surface.The author is indebted to Prof. M. Jaroniec for very fruitful discussions and to Prof. J. Choma for the activated carbon samples.     

Adsorption of organic molecules on silica surface

The adsorption behaviour of various organic adsorbates on silica surface is reviewed. Most of the structural information on silica is obtained from IR spectral data and from the characteristics of water present at the silica surface. Silica surface is generally embedded with hydroxy groups and ethereal linkages, and hence considered to have a negative charged surface prone to adsorption of electron deficient species. Adsorption isotherms of the adsorbates delineate the nature of binding of the adsorbate with silica. Aromatic compounds are found to involve the pi-cloud in hydrogen bonding with silanol OH group during adsorption. Cationic and nonionic surfactants adsorb on silica surface involving hydrogen bonding. Sometimes, a polar part of the surfactants also contributes to the adsorption process. Styryl pyridinium dyes are found to anchor on silica surface in flat-on position. On modification of the silica by treating with alkali, the adsorption behaviour of cationic surfactant or polyethylene glycol changes due to change in the characteristics of silica or modified silica surface. In case of PEG-modified silica, adsolubilization of the adsorbate is observed. By using a modified adsorption equation, hemimicellization is proposed for these dyes. Adsorptions of some natural macromolecules like proteins and nucleic acids are investigated to study the hydrophobic and hydrophilic binding sites of silica. Artificial macromolecules like synthetic polymers are found to be adsorbed on silica surface due to the interaction of the multifunctional groups of the polymers with silanols. Preferential adsorption of polar adsorbates is observed in case of adsorbate mixtures. When surfactant mixtures are considered to study competitive adsorption on silica surface, critical micelle concentration of individual surfactant also contributes to the adsorption isotherm. The structural study of adsorbed surface and the thermodynamics of adsorption are given some importance in this review.     

Adsorption of pure and mixed solvent solutions of spin probes onto stationary phases

Water, methanol (MeOH), acetonitrile (ACN), and binary MeOH-water and ACN-water solutions of different spin probes (nitroxides), selected to mimic the behavior of different pollutants, were adsorbed onto stationary phases usually used in reversed-phase high-performance liquid chromatography (RP-HPLC). These stationary phases are constituted by porous silica and differ from each other regarding the surface area, the pore size, the particle size, the surface functions (NH2, C8, and C18), and the percentage of functionalization. The electron paramagnetic resonance (EPR) spectra of the probe solutions adsorbed into the pores were analyzed by computer-aided computation of the spectral line shape, which provided structural and dynamical parameters of the probes and their environments. These parameters provided information on the surface properties of the stationary phases, such as alkyl chain density, solvent penetration, stationary-phase ordering, and residual silanol effects, which modify the retention times in HPLC. A different availability of polar surface groups in the pure and mixed solvents was found for the different stationary phases depending on (1) the different functionalization degree, (2) the surface-chain length, (3) the particle size, and (4) the polarity of both the probe and the solvent. The C8 functionalization rendered the surface more hydrophobic with respect to C18. The endcapping process of the residual silanols strongly enhanced the surface hydrophobicity tested by the probes. At the highest water content, the adsorption of the polar or charged probes onto the hydrophobic surface is the lowest and self-aggregation occurs. When the probes bear both hydrophilic and hydrophobic moieties, the adsorption is enhanced by a synergy between hydrophilic and hydrophobic bonds with the surface. A balance between the hydrophilic and hydrophobic forces leads to high adsorption and partial insertion of the surfactant probes in an ordered C18 chain layer at the solid surface which forms in the binary mixtures; this layer is ascertained between 40% and 70% of the less hydrophilic solvent, depending on the type of both the solid and the probe. This insertion and the response on the formation of the ordered layer were favored in ACN-water with respect to MeOH-water.     

聚乙烯在羟基化β-石英(100)表面上的有序吸附

利用分子动力学模拟方法研究了聚乙烯链在羟基化β-石英(100)表面上的吸附. 结果表明, 吸附基底上的规则图案起到模板的作用, 无论是真空还是溶液环境, 都会引导聚乙烯链在表面形成二维沿着[110]方向取向的折叠构型. 为了与聚乙烯的吸附相比较, 进一步研究了聚氧化乙烯链在相同表面上的吸附情况. 结果表明, 极性链与非极性链在极性表面上的吸附情况完全不同.     

Estimation of Adsorption Layer Capacity by Sandwich Thin-Layer Chromatography

Abstract

The use of sandwich tanks with a capillary solvent delivery system permits the determination of the volume of the developing solvent in the adsorbent layer as well as the position of the solvent demixing front. Therefore, the adsorption isotherms of polar solvents from solutions in nonpolar diluents and the adsorption layer capacities can be determined in a simple manner, analogous to the column technique: Instead of determination of breakthrough volume, the solvent demixing front on the thin layer is localized by means of a series of test dyes whose spots flatten and merge on the steep solvent composition gradient. The method is illustrated for nine aliphatic ketones adsorbed from heptane and benzene solutions. The experimental results indicate different modes of adsorption from solutions in the two diluents; the surface areas corresponding to one solute molecule are also different for symmetrical dialkyl ketones and isomeric methyl-alkyl ketones.     

Study of adsorption behavior of bilirubin on human-albumin monolayer using a quartz crystal microbalance

The quartz crystal microbalance was employed to study the adsorption behavior of bilirubin on human-albumin layer, which was chemically bound to the self-assembled monolayer of 4-aminothiophenol on the surface of a gold electrode of the crystal via glutaraldehyde. A long-time adsorption process of bilirubin that took place on a human-albumin-modified surface was observed, and the adsorption kinetic parameters were estimated from the in situ frequency measurements. The amount of adsorbed bilirubin increased with increasing of both hydrogen ions and bilirubin concentration and was larger than that estimated based on the conclusion that there are two affinity sites for bilirubin per albumin molecule. With the present method, the displacement of bilirubin from an albumin layer caused by aspirin was also examined. QCM measurement provides a facile method for in situ monitoring of the adsorption/desorption of bilirubin on proteins layers.     

Characterization of the interaction between gelatin and a spread monolayer of octadecanoic acid

Surface rheological measurements of octandecanoic acid monolayers spread on gelatin solutions were performed. The interaction of the spread monolayer with the gelatin involves a strong rise of the solidity of the surface structure with distinct viscoelastic properties and is comparable with the experimental findings looking into the interaction between gelatin and an ionic surfactant. The results found by the addition of sodium-dodecylsulfate to the gelatin solution are discussed, assuming the formation of a multilayer consisting of octadecanoic acid molecules interacting to a negligible degree with the gelatin-surfactant complexes displaced from the surface. The surface rheological parameters are influenced by both layers in opposition to the dynamic behaviour at compression and dilation described in the first part of this paper. An analogous effect is found if the cationic hexadecyltrimethylammoniurn-bromide is added to the gelatin solution. The influence of CTAB is interpreted as the consequence of a steric hindrance, caused by the concentration of groups with opposite charges on the small polar ranges of the gelatin molecules. As a particular interaction of octadecanoic acid with the complexes is possible, a mixed adsorption layer is formed and the high solidity of the surface layer is prevented by the presence of molecules not interacting with the complexes.     

Biofouling-resistance expanded poly(tetrafluoroethylene) membrane with a hydrogel-like layer of surface-immobilized poly(ethylene glycol) methacrylate for human plasma protein repulsions

In general, it is a challenge to control the highly polar material grafting from the chemically inert Teflon-based membrane surface. This work describes the surface modification and characterization of expanded poly(tetrafluoroethylene) (ePTFE) membranes grafted with poly(ethylene glycol) methacrylate (PEGMA) macromonomer via surface-activated plasma treatment and thermally induced graft copolymerization. The chemical composition and microstructure of the surface-modified ePTFE membranes were characterized by Fourier transform infrared spectroscopy (FT-IR), contact angle, and bio-atomic force microscopy (bio-AFM) measurements. Biofouling property of the modified membranes was evaluated by the measurements of the plasma protein (γ-globulin, fibrinogen, or albumin) adsorption determined using an enzyme-linked immunosorbent assay (ELISA). In general, the hydrophilicity of the surface of ePTFE membranes increases with increasing the grafting degree of the copolymerized PEGMA. The highly hydrated PEGMA chain on the resulting ePTFE membranes was found to form a surface hydrogel-like layer with regulated coverage in aqueous state, which can be controlled by the content of PEGMA macromonomer in the reaction solution. The relative protein adsorption was effectively reduced with increasing capacity of the hydration for the PEGMA chain grafted on the ePTFE membrane surface. From both results of protein adsorption and platelet adhesion test in vitro, it is concluded that the PEGMA-grafted hydrophilic ePTFE membranes could provide good biofouling resistance to substantially reduce plasma protein and blood platelet fouling on the membrane surface in human body temperature.     

γ-Fe2O3的表面润湿性与其悬浮液的稳定性

自吸附与表面润湿性的测量确定,油酸钠自水溶液在γ-Fe₃O₂上的吸附为多层吸附。第一层为化学吸附,油酸钠分子的碳氢链朝外,从而使质点表面憎水化。在高浓度时发生第二层吸附,油酸钠分子依靠碳氢链之间的相互作用吸附在第一吸附层上,使质点表面重新亲水化。质点表面的润湿性与其水相和非水相悬浮液的稳定性有直接的对应关系。     

Adsorption of dodecyltrimethylammonium bromide and sodium bromide on gold studied by liquid chromatography and flow adsorption microcalorimetry

Here, we report on a new aspect of the adsorption of Br- on the surface of gold. The adsorption of dodecyltrimethylammonium bromide (C12TABr) from aqueous solutions onto macroporous gold particles was studied by continuous flow frontal analysis solid/liquid chromatography and flow adsorption microcalorimetry. The material balance and enthalpy balance of adsorption and the change in the solution pH were measured simultaneously. Initially, Br- is irreversibly bound to high-affinity surface sites counterbalanced by the adsorption of H+ from the aqueous phase. The surface speciation is accompanied by the formation of C12TAOH, which in turn results in a significant pH increase in the bulk solution. The net process was found to be strongly exothermic (-280 kJ.mol(-1)), which is indicative of the occurrence of chemisorption. The specific adsorption of Br- is followed by the reversible adsorption of C12TABr to produce a firmly bound monolayer in a head-to-surface arrangement (-53 kJ.mol(-1)). In a relatively narrow range of the surface coverage, various composite structures may develop on the top layer and eventually transform to full-cylindrical surface aggregates. The surface aggregation was found to be reversible, with an enthalpy change of -11 kJ.mol(-1). The importance of the specific binding of Br- to the surface of gold was confirmed by measurement of the initial adsorption of NaBr on the microparticles. The initial adsorption was found to be irreversible, with an enthalpy change of approximately -240 kJ.mol(-1). This process involved the formation of an AuBr-/H+ electric double layer at the gold/water interface, accompanied by a dramatic increase in the solution pH due to the release of a copious amount of OH- in the bulk liquid phase.     

Acid/Base Properties and Adsorption of an Azo Dye on Coating Pigments

Adsorption of an anionic disazo dye, Food Black 2 on coating pigments from polar solvents was studied. Pigments (kaolin, precipitated CaCO₃, amorphous SiO₂, TiO₂, Al₂O₃, and talc) were chosen to be representative of those used in paper for ink‐jet printing. The predominating driving force for the adsorption was electrostatic interactions for all the pigments except talc, for which hydrophobic interactions were dominant. Lewis acid‐base properties of the pigments were studied by measuring adsorption of Lewis acid‐probe molecules from both polar and nonpolar media. The pigments studied were found to be amphoteric, containing both acidic and basic surface groups. However, in the presence of polar solvents, the adsorption of acid‐base probe molecules was greatly reduced, which indicates that Lewis acid‐base interactions have only a small influence on the adsorption of azo dyes from polar media such as water.